CN116194845A

CN116194845A - Photomask, exposure method, method for producing resin pattern, and method for producing photomask

Info

Publication number: CN116194845A
Application number: CN202180055266.4A
Authority: CN
Inventors: 汉那慎一; 两角一真
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-08-31
Filing date: 2021-07-07
Publication date: 2023-05-30
Also published as: WO2022044557A1; TW202225823A; JPWO2022044557A1

Abstract

The invention provides a photomask and application thereof, wherein the photomask comprises: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; and a light shielding layer disposed on a part of the 1 st surface of the transparent support, wherein the exposed part of the 1 st surface has a surface roughness Rz of 0.1 μm to 0.5 μm, and the light shielding layer has a surface roughness Rz of 0.1 μm to 0.5 μm.

Description

Photomask, exposure method, method for producing resin pattern, and method for producing photomask

Technical Field

The present invention relates to a photomask, an exposure method, a method for manufacturing a resin pattern, and a method for manufacturing a photomask.

Background

As an exposure method in photolithography, for example, a method of exposing a photosensitive layer by bringing a photomask into contact with the photosensitive layer is known. As described above, the method of exposing a photomask to an object by bringing the photomask into contact with the object is called contact exposure. The contact exposure shortens the distance between the photomask and the photosensitive layer and improves the resolution. The exposed photosensitive layer is developed to form a desired pattern. If the photomask is brought into contact with the photosensitive layer, for example, a problem may occur in that the photosensitive layer adheres to the photomask. In order to solve the above-described problem, patent document 1 discloses a photomask having a release layer thicker than a light shielding pattern. When the photomask disclosed in patent document 1 is brought into contact with the photosensitive layer, the release layer is closely adhered to the photosensitive layer, but the light shielding pattern is not closely adhered to the photosensitive layer. As a result, the photomask can be smoothly separated from the photosensitive layer. However, according to the photomask disclosed in patent document 1, since the distance between the photomask and the photosensitive layer becomes long, the resolution is lowered. In order to solve the above-mentioned problems, patent document 2 discloses a photomask for performing exposure in a state of contact with a resist, wherein a rough surface region is provided on a surface on a side of contact with the resist.

Patent document 1: japanese patent laid-open No. 8-6235

Patent document 2: japanese patent laid-open No. 2006-18190

Disclosure of Invention

Technical problem to be solved by the invention

According to the photomask disclosed in patent document 2, the distance between the photomask and the photosensitive layer becomes short. On the other hand, in the exposure method using a roughened photomask, linearity of the obtained pattern may be lowered. In contact exposure, it is required to improve the linearity of the resulting pattern while reducing the adhesiveness of the photomask to a contact object such as a photosensitive layer.

An object of one embodiment of the present invention is to provide a photomask in which adhesiveness to a contact object during contact exposure is reduced, and a pattern having excellent linearity is formed.

Another object of the present invention is to provide an exposure method using the photomask.

Another object of the present invention is to provide a method for producing a resin pattern using the photomask.

Another object of the present invention is to provide a method for manufacturing a photomask in which adhesiveness to a contact object during contact exposure is reduced, and a pattern having excellent linearity is formed.

Means for solving the technical problems

The present invention includes the following means.

<1> a photomask, comprising: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; and a light shielding layer disposed on a part of the 1 st surface of the transparent support, wherein the exposed part of the 1 st surface has a surface roughness Rz of 0.1 μm to 0.5 μm, and the light shielding layer has a surface roughness Rz of 0.1 μm to 0.5 μm.

<2> the photomask according to <1>, wherein the exposed portion of the 1 st surface has a surface roughness Ra of 5nm to 50nm and the light shielding layer has a surface roughness Ra of 5nm to 50nm.

<3> a photomask, comprising: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; a light shielding layer disposed on a part of the 1 st surface of the transparent support; and a protective layer disposed on the 1 st surface of the transparent support and the light shielding layer, wherein a surface roughness Rz of the protective layer is 0.1 μm to 0.5 μm.

<4> the photomask according to <3>, wherein the surface roughness Ra of the protective layer is 5nm to 50nm.

<5> the photomask according to <3> or <4>, wherein the protective layer contains an organic polymer compound.

<6> the photomask according to <5>, wherein the organic polymer compound contains a structural unit derived from urethane acrylate.

<7> the photomask according to any one of <3> to <6>, wherein the protective layer contains a fluorine atom-containing compound.

<8> the photomask according to any one of <1> to <7>, wherein the transparent support is a plate-shaped quartz glass.

<9> the photomask according to any one of <1> to <8>, wherein the light shielding layer contains chromium.

<10> an exposure method comprising the steps of: preparing a photomask of any of <1> to <9 >; and exposing the photosensitive layer with the photomask in between by bringing the photomask into contact with the photosensitive layer.

<11> a method for producing a resin pattern, comprising the steps of: preparing a photomask of any of <1> to <9 >; exposing the photosensitive layer with the photomask in between by bringing the photomask into contact with the photosensitive layer; and developing the exposed photosensitive layer to form a resin pattern.

<12> a method for producing a resin pattern, comprising the steps of: preparing a photomask of any of <1> to <9 >; preparing a laminate comprising a photosensitive layer and a temporary support in this order; exposing the photosensitive layer to light through the photomask and the temporary support while the photomask and the temporary support are in contact with each other; and developing the exposed photosensitive layer to form a resin pattern.

<13> a method for producing a resin pattern, comprising the steps of: preparing a photomask of any of <1> to <9 >; preparing a laminate comprising a photosensitive layer and a temporary support in this order; peeling the temporary support to expose the surface of the photosensitive layer; exposing the photosensitive layer with the photomask interposed therebetween by bringing the photomask into contact with the surface of the photosensitive layer exposed by the peeling of the temporary support; and developing the exposed photosensitive layer to form a resin pattern.

<14>According to<12>Or (b)<13>In the method for producing a resin pattern, the laminate further includes a resin layer between the photosensitive layer and the temporary support,the resin layer has a universal hardness (universal hardness) of 5.0N/mm, as measured by a test load when the press-in depth is 1/10 of the thickness of the resin layer in a press-in test ² In the above, when the photosensitive layer is exposed, the photosensitive layer is exposed with the photomask and the resin layer interposed therebetween.

<15> the method for producing a resin pattern according to <14>, wherein the resin layer contains polyvinyl alcohol.

<16>According to<11>To the point of<15>The method for producing a resin pattern according to any one of the above, wherein the general hardness of the photosensitive layer measured according to a test load when the press-in depth in the press-in test is 1/10 of the thickness of the photosensitive layer is 5.0N/mm ² The above.

<17> a method for manufacturing a photomask, comprising the steps of: preparing a laminate including a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface, and a light shielding layer disposed on a part of the 1 st surface of the transparent support; and performing a blast (blast) treatment on the laminate to adjust the surface roughness Rz of the exposed portion of the 1 st surface to 0.1 μm to 0.5 μm and the surface roughness Rz of the light shielding layer to 0.1 μm to 0.5 μm.

<18> a method for manufacturing a photomask, comprising the steps of: preparing a laminate including a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface, a light shielding layer disposed on a part of the 1 st surface of the transparent support, and a protective layer disposed on the 1 st surface of the transparent support and the light shielding layer; and performing sandblasting treatment on the laminated body to adjust the surface roughness Rz of the protective layer to be 0.1-0.5 mu m.

<19> the method for manufacturing a photomask according to <17> or <18>, wherein the blasting is wet blasting.

Effects of the invention

According to one aspect of the present invention, there is provided a photomask in which adhesiveness to a contact object during contact exposure is reduced, and a pattern having excellent linearity is formed.

According to another aspect of the present invention, there is provided an exposure method using the above photomask.

According to another aspect of the present invention, there is provided a method for manufacturing a resin pattern using the photomask.

According to another aspect of the present invention, there is provided a method for manufacturing a photomask in which adhesiveness to a contact object in contact exposure is reduced to form a pattern having excellent linearity.

Drawings

Fig. 1 is a schematic cross-sectional view showing a layer structure of a photomask according to embodiment 1.

Fig. 2 is a schematic cross-sectional view showing a layer structure of the photomask according to embodiment 1 in contact with a photosensitive layer.

Fig. 3 is a schematic cross-sectional view showing a layer structure of the photomask according to embodiment 2.

Fig. 4 is a schematic cross-sectional view showing a layer structure of a photomask according to embodiment 2 in contact with a photosensitive layer.

Detailed Description

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. The following embodiments may be appropriately modified within the scope of the object of the present invention.

In the description of the embodiments of the present invention with reference to the drawings, the description of the repeated constituent elements and symbols may be omitted. The constituent elements denoted by the same reference numerals in the drawings refer to the same constituent elements. The ratio of dimensions in the drawings does not necessarily represent the ratio of actual dimensions.

In the present invention, the numerical range indicated by the term "to" refers to a range in which the numerical values described before and after the term "to" are included as a lower limit value and an upper limit value. In the present invention, an upper limit value or a lower limit value representing a certain numerical range may be replaced with an upper limit value or a lower limit value representing another numerical range. In the present invention, the upper limit value or the lower limit value representing a certain numerical range may be replaced with the value shown in the embodiment.

In the present invention, "(meth) acrylic" means acrylic acid, methacrylic acid or both acrylic acid and methacrylic acid.

In the present invention, "(meth) acrylate" means acrylate, methacrylate, and both acrylate and methacrylate.

In the present invention, the amounts of the respective components in the composition, when a plurality of substances corresponding to the respective components are present in the composition, refer to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified.

In the present invention, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved.

The expression of the group (atomic group) in the present invention is not described that the substituted and unsubstituted expressions include a group having no substituent and a group having a substituent. For example, "alkyl" contains not only an alkyl group having no substituent (i.e., an unsubstituted alkyl group) but also an alkyl group having a substituent (i.e., a substituted alkyl group).

In the present invention, unless otherwise specified, "exposure" includes not only exposure using light but also a description using a particle beam such as an electron beam or an ion beam. The light used for exposure generally includes an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), active rays (active energy rays) such as X-rays and electron beams.

In the present invention, the chemical structural formula is sometimes described by a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "mass%" and "weight%" are synonymous, and "part by mass" and "part by weight" are synonymous.

In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights in terms of polystyrene using a Gel Permeation Chromatography (GPC) analysis device, tetrahydrofuran as a solvent, and a differential refractometer. The columns used in the GPC analysis equipment were "TSK. Mu.l GMHxL, TSK. Mu.l G4000HxL" and "TSKgel G2000HxL" (both trade names manufactured by TOSOH CORPORATION).

In the present invention, ordinal words (for example, "1 st" and "2 nd") are terms used to distinguish components, and do not limit the number of components and the merits of the components.

< photomask >

Embodiment 1

A photomask according to an embodiment of the present invention includes: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; and a light shielding layer on a part of the 1 st surface of the transparent support. The surface roughness Rz of the exposed part of the 1 st surface is 0.1 to 0.5 mu m, and the surface roughness Rz of the light shielding layer is 0.1 to 0.5 mu m. According to the above embodiment, there is provided a photomask in which adhesiveness to a contact object in contact exposure is reduced, and a pattern having excellent linearity is formed. Hereinafter, the photomask according to the above embodiment will be referred to as "photomask according to embodiment 1".

The reason why the photomask according to embodiment 1 exhibits the above-described effect will be described below with reference to fig. 1 and 2. Fig. 1 is a schematic cross-sectional view showing a layer structure of a photomask according to embodiment 1. Fig. 2 is a schematic cross-sectional view showing a layer structure of the photomask according to embodiment 1 in contact with a photosensitive layer.

The photomask 100 shown in fig. 1 includes a transparent support 10 and a light-shielding layer 20. The transparent support 10 has a 1 st surface 10a and a 2 nd surface 10b. A part of the 1 st surface 10a is covered with a light shielding layer 20. The surface roughness Rz of the exposed portion of the 1 st surface 10a (in other words, the portion of the 1 st surface 10a not covered with the light shielding layer 20) is 0.1 μm to 0.5 μm. The 2 nd surface 10b is a surface located on the opposite side from the 1 st surface 10 a. The light shielding layer 20 is disposed on a part of the 1 st surface 10a of the transparent support 10. The surface roughness Rz of the light shielding layer 20 is 0.1 μm to 0.5 μm.

As shown in fig. 2, the photomask 100 is used in contact with the photosensitive layer 200. The surface roughness Rz of the portion of the photomask 100 in contact with the photosensitive layer 200 is adjusted to 0.1 μm to 0.5 μm. The light shielding layer 20 of the photomask 100 is in contact with the photosensitive layer 200. In fig. 2, the 1 st surface 10a of the photomask 100 is not in contact with the photosensitive layer 200 in order to clarify the layer structure. However, the matter shown in fig. 2 does not exclude the case where the 1 st surface 10a of the photomask 100 is in contact with the photosensitive layer 200. The 1 st surface 10a of the photomask 100 may be in contact with the photosensitive layer 200. In the exposure method of the photosensitive layer 200 using the photomask 100, the photomask 100 is brought into contact with the photosensitive layer 200, and then the photosensitive layer 200 is exposed with the photomask 100 interposed therebetween. Light irradiated from the light source transmits the portion of the transparent support 10 not covered with the light shielding layer 20. After exposing the photosensitive layer 200, the photomask 100 is peeled off from the photosensitive layer 200. Hereinafter, a portion of the transparent support not covered with the light shielding layer may be referred to as a "light transmitting portion".

As described above, in the exposure method of the photosensitive layer using the photomask according to embodiment 1, the portion (for example, the transparent support and the light shielding layer) having the surface roughness Rz of 0.1 μm to 0.5 μm in the photomask according to embodiment 1 is brought into contact with the object (for example, the photosensitive layer). In the photomask according to embodiment 1, the surface roughness Rz of the portion in contact with the object to be contacted is 0.1 μm to 0.5 μm, whereby the smoothness of the photomask is improved and scattering of light during exposure is suppressed. The smoothness of the photomask is improved, and the adhesiveness of the photomask to the photosensitive layer is reduced. Scattering of light during exposure is suppressed, and linearity of the obtained pattern is improved. Therefore, according to an embodiment of the present invention, there is provided a photomask in which adhesiveness to a contact object in contact exposure is reduced, and a pattern having excellent linearity is formed. Hereinafter, the photomask according to embodiment 1 will be described in detail.

[ transparent support ]

The photomask according to embodiment 1 includes a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface. In the present invention, "transparent" means that the transmittance of light in the wavelength region of 350nm to 700nm is 50% or more. The transmittance of the light is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. The transmittance of the light may be 100% or less than 100%. The transmittance of light was measured using an ultraviolet-visible spectrophotometer (e.g., UV1800 manufactured by Shimadzu Corporation). Hereinafter, the transparent support of the photomask according to embodiment 1 will be described in detail.

Examples of the transparent support include quartz glass, soda lime glass, and PET film. The transparent support is preferably quartz glass from the viewpoints of transmittance and dimensional accuracy.

The transparent support is preferably flat.

The thickness of the transparent support is not limited. From the viewpoint of strength, the thickness of the transparent support is preferably 0.5mm or more, more preferably 1mm or more, and particularly preferably 2mm or more. From the viewpoint of transmittance, the thickness of the transparent support is preferably 5mm or less, more preferably 4mm or less, and particularly preferably 3mm or less. The thickness of the transparent support is determined by arithmetically averaging the thickness of the transparent support measured at 10.

The 1 st surface of the transparent support is a surface on which the light shielding layer is disposed. The 1 st surface of the transparent support faces the light shielding layer. The surface roughness Rz of the exposed part of the 1 st surface is 0.1-0.5 mu m. The "exposed portion of the 1 st surface" means a portion of the 1 st surface not covered with the light shielding layer. When the surface roughness Rz of the exposed portion of the 1 st surface is 0.1 μm or more, the smoothness of the photomask is improved, and the adhesiveness of the photomask to the object to be contacted during contact exposure is reduced. When the surface roughness Rz of the exposed portion of the 1 st surface is 0.5 μm or less, scattering of light during exposure is suppressed, and the linearity of the obtained pattern is improved. The surface roughness Rz of the exposed portion of the 1 st surface is preferably 0.15 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.25 μm or more, from the viewpoint of reducing the adhesiveness of the photomask to a contact object during contact exposure. The surface roughness Rz of the exposed portion of the 1 st surface is preferably 0.45 μm or less, more preferably 0.4 μm or less, and particularly preferably 0.35 μm or less from the viewpoint of improving the linearity of the pattern.

In the present invention, the term "surface roughness Rz" refers to a value obtained by expressing the sum of the maximum value of the height of the mountain and the maximum value of the depth of the valley observed in the roughness curve at the reference length in micrometers. Hereinafter, a method for measuring the surface roughness Rz will be specifically described. A roughness curve on the surface of the object to be measured and an average line of the roughness curve are prepared using a surface roughness measuring device (for example, VK-X1000 manufactured by KEYENCE CORPORATION). A portion corresponding to the reference length is extracted from the roughness curve. The surface roughness Rz of the object to be measured is measured by obtaining the total value of the maximum value of the height of the mountain (i.e., the height from the average line to the mountain top) and the maximum value of the depth of the valley (i.e., the height from the average line to the valley bottom) observed in the extracted roughness curve.

The surface roughness Ra of the exposed portion of the 1 st surface is preferably 5nm to 50nm. When the surface roughness Ra of the exposed portion of the 1 st surface is 5nm or more, the smoothness of the photomask is improved, and the adhesiveness of the photomask to the object to be contacted during contact exposure is reduced. When the surface roughness Ra of the exposed portion of the 1 st surface is 50nm or less, scattering of light during exposure is suppressed, and the linearity of the obtained pattern is improved. The surface roughness Ra of the exposed portion of the 1 st surface is preferably 10nm or less, more preferably 15nm or more, and particularly preferably 20nm or more, from the viewpoint of reducing the adhesiveness of the photomask to a contact object during contact exposure. From the viewpoint of improving the linearity of the pattern, the surface roughness Ra of the exposed portion of the 1 st surface is preferably 40nm or less, more preferably 35nm or less, and particularly preferably 30nm or less.

In the present invention, the term "surface roughness Ra" refers to a value expressed in nanometers as an arithmetic average roughness calculated from a roughness curve at a reference length. Hereinafter, a method for measuring the surface roughness Ra will be specifically described. A roughness curve on the surface of the object to be measured and an average line of the roughness curve are prepared using a surface roughness measuring device (for example, VK-X1000 manufactured by KEYENCE CORPORATION). A portion corresponding to the reference length is extracted from the roughness curve. The surface roughness Ra is measured by calculating an arithmetic average roughness from the extracted roughness curve. The calculation of the arithmetic average roughness (Ra) is described in "JIS B0601: 2017".

[ light-shielding layer ]

The photomask according to embodiment 1 includes a light-shielding layer. In the present invention, "light shielding" means that the transmittance of light in the wavelength region of 350nm to 700nm is 1% or less. The transmittance of the light is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The transmittance of light was measured using an ultraviolet-visible spectrophotometer (e.g., UV1800 manufactured by Shimadzu Corporation). Hereinafter, the light shielding layer of the photomask according to embodiment 1 will be described in detail.

The light shielding layer is disposed on a part of the 1 st surface of the transparent support. The photosensitive layer can be exposed in a pattern through a photomask by disposing the light shielding layer on a part of the 1 st surface of the transparent support. The position of the light shielding layer can be determined, for example, by the shape of a pattern formed by photolithography.

The composition of the light shielding layer is not limited. Examples of the component of the light-shielding layer include chromium and blackened metallic silver. The light-shielding layer preferably contains chromium.

The surface roughness Rz of the light shielding layer is 0.1-0.5 mu m. By setting the surface roughness Rz of the light shielding layer to 0.1 μm or more, the smoothness of the photomask is improved, and the adhesiveness of the photomask to a contact object during contact exposure is reduced. By setting the surface roughness Rz of the light shielding layer to 0.5 μm or less, scattering of light during exposure is suppressed, and the linearity of the obtained pattern is improved. The surface roughness Rz of the light shielding layer is preferably 0.15 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.25 μm or more from the viewpoint of reducing the adhesiveness of the photomask to a contact object during contact exposure. From the viewpoint of improving the linearity of the pattern, the surface roughness Rz of the light shielding layer is preferably 0.45 μm or less, more preferably 0.4 μm or less, and particularly preferably 0.35 μm or less. Further, from the viewpoint of improving the linearity of the pattern, the surface roughness Rz of the light shielding layer is preferably 0.3 μm or less, more preferably 0.25 μm or less. The surface roughness Rz of the light shielding layer may be the same as or different from the surface roughness Rz of the exposed portion of the 1 st surface of the transparent support.

The surface roughness Ra of the light-shielding layer is preferably 5nm to 50nm. By the surface roughness Ra of the light shielding layer being 5nm or more, the smoothness of the photomask is improved, and the adhesiveness of the photomask to a contact object during contact exposure is reduced. The surface roughness Ra of the light shielding layer is 50nm or less, whereby scattering of light during exposure is suppressed and linearity of the obtained pattern is improved. The surface roughness Ra of the light shielding layer is preferably 10nm or less, more preferably 15nm or more, and particularly preferably 20nm or more, from the viewpoint of reducing the adhesiveness of the photomask to a contact object during contact exposure. From the viewpoint of improving the linearity of the pattern, the surface roughness Ra of the light shielding layer is preferably 40nm or less, more preferably 35nm or less, and particularly preferably 30nm or less. The surface roughness Ra of the light shielding layer may be the same as or different from the surface roughness Ra of the exposed portion of the 1 st surface of the transparent support.

The thickness of the light shielding layer is not limited. The thickness of the light-shielding layer is preferably smaller than the thickness of the transparent support. From the viewpoint of light-shielding properties, the thickness of the light-shielding layer is preferably 50nm or more, more preferably 80nm or more, and particularly preferably 100nm or more. The thickness of the light shielding layer is preferably 300nm or less, more preferably 250nm or less, and particularly preferably 200nm or less, from the viewpoints of dust accumulation and removal due to a level difference from the exposed portion. The thickness of the light-shielding layer was measured by arithmetically averaging the thicknesses of the light-shielding layer measured at 10.

[ method of production ]

As a method for manufacturing a photomask according to embodiment 1, for example, the following method can be mentioned: the surface of the transparent support and the surface of the light shielding layer are roughened using a laminate comprising the transparent support and the light shielding layer. In one embodiment, the method for manufacturing a photomask preferably includes a 1 st preparation step and a 1 st roughening step. In the 1 st preparation step, a laminate is prepared, the laminate including: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; and a light shielding layer disposed on a part of the 1 st surface of the transparent support. In the 1 st roughening step, the laminate is subjected to a blasting treatment to adjust the surface roughness Rz of the exposed portion of the 1 st surface to 0.1 μm to 0.5 μm and the surface roughness Rz of the light shielding layer to 0.1 μm to 0.5 μm. Further, the method for manufacturing a photomask more preferably includes a 2 nd preparation step and a 2 nd roughening step. In the 2 nd preparation step, a laminate is prepared, the laminate including: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; and a light shielding layer disposed on a part of the 1 st surface of the transparent support. In the 2 nd roughening step, the laminate is subjected to a blasting treatment to adjust the surface roughness Rz of the exposed portion of the 1 st surface to 0.1 μm to 0.5 μm, the surface roughness Ra of the exposed portion of the 1 st surface to 5nm to 50nm, the surface roughness Rz of the light shielding layer to 0.1 μm to 0.5 μm, and the surface roughness Ra of the light shielding layer to 5nm to 50nm. Hereinafter, a method for manufacturing a photomask according to embodiment 1 will be described in detail.

(laminate)

The laminate used in the method for producing a photomask can be produced by a known method for producing a photomask, for example. For example, a material is prepared by (1) comprising a transparent support, a light shielding layer, and a resist in this order; (2) exposure of the resist; (3) Developing the resist, (4) removing the exposed light shielding layer; and (5) removing the resist, whereby a laminate can be produced.

Examples of the method for forming the light shielding layer include sputtering.

In the method for producing a photomask, for example, a known photomask can be used as the laminate. Examples of the photomask that can be used as the laminate include a chromium mask provided with a metallic chromium layer and an emulsion mask provided with a silver halide emulsion layer described in "photolithography" (published by japan photolithography and processing institute, edited by educational literature, pages 67 to 80, and month 6 in 1992). In the method for manufacturing a chromium mask, for example, the chromium mask can be manufactured by the following steps: (1) Forming a chromium layer on a transparent support such as quartz and soda glass by sputtering; (2) Processing the etching resist formed on the chromium layer into a pattern by exposure and development; (3) etching the chromium layer; and (4) removing the etch resist. The exposure of the etching resist can be performed using, for example, helium cadmium (HeCd) laser (wavelength: 442 nm). The development of the etching resist can be performed using an aqueous alkali solution, for example.

(Sand blasting)

The blasting is a treatment for processing a solid surface using an abrasive material. Examples of the blasting include dry blasting and wet blasting. The blasting is preferably wet blasting.

Dry blasting

Dry blasting is known as a method for using a powder or granule as an abrasive. According to the dry blasting, the powder particle collides with the surface of the object to change the property or shape of the surface of the object.

In the dry blasting treatment, for example, hard powder particles having an acute-angled polygon shape can be used as the powder particles. As the powder, a powder having a relatively high specific gravity is preferable. Examples of the powder particles include alumina, silicon carbide, silica, silicon rock, metal powder (e.g., iron, nickel, aluminum, and stainless steel), and metal oxide (e.g., zrO) ₂ 、Al ₂ O ₃ 、SiO ₂ ). The particle size of the powder is preferably 20 to 350 mesh. However, the particle size of the powder is not limited to the above-mentioned values. The particle size of the powder or granule is preferably determined according to the type of the object and the conditions of the dry blasting.

In the dry blasting, for example, a blasting device using compressed air or a projection device using centrifugal force is used to collide the powder with the object. Preferred conditions of the dry blasting using the blasting apparatus are shown below. However, the conditions of the dry blasting treatment are not limited to the following conditions. The preferable conditions for dry blasting can be determined, for example, by the type of powder, the particle size of the powder, and the type of object. The conditions of the dry blasting treatment may be determined according to known conditions of the dry blasting treatment.

(1) Diameter of the spray nozzle: 2mm to 10mm

(2) Pressure of compressed air: 1kg/cm ² ～10kg/cm ²

(3) Jet distance: 5cm to 30cm

(4) Injection time: 10 seconds/m ² About 1000 seconds/m ²

Wet blasting

Wet blasting is known as a method of spraying slurry containing an abrasive material from a spray nozzle using the force of compressed air. Examples of the polishing material include inorganic particles and a polishing agent in which inorganic particles and a resin are integrated. Examples of the inorganic particles used as the polishing material include alumina, silicon carbide, glass, and zirconia. From the viewpoint of the treatment effect, alumina is preferable. Examples of the shape of the polishing material include a polygonal shape and a spherical shape (for example, a spherical shape is included). The central particle diameter of the polishing material is preferably 3 μm to 50. Mu.m, more preferably 5 μm to 30. Mu.m, particularly preferably 5 μm to 20. Mu.m.

The slurry can be produced, for example, by mixing the abrasive material with a solvent (e.g., water). The concentration of the abrasive material in the slurry is preferably 1 to 50% by volume, more preferably 2 to 30% by volume, and particularly preferably 3 to 20% by volume. The concentration of the abrasive is calculated based on the volume of the slurry.

The air pressure of the compressed air is preferably 0.1 to 1MPa, more preferably 0.1 to 0.8MPa, and particularly preferably 0.1 to 0.5MPa.

The treatment speed is preferably 5 mm/sec to 100 mm/sec, more preferably 20 mm/sec to 100 mm/sec, and particularly preferably 35 mm/sec to 100 mm/sec.

The conditions of the wet blasting treatment are not limited to the above conditions. The conditions of the wet blasting treatment may be determined according to known conditions of the wet blasting treatment.

Embodiment 2

A photomask according to an embodiment of the present invention includes: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; a light shielding layer disposed on a part of the 1 st surface of the transparent support; and a protective layer disposed on the 1 st surface of the transparent support and the light shielding layer. The surface roughness Rz of the protective layer is 0.1-0.5 mu m. According to the above embodiment, there is provided a photomask in which adhesiveness to a contact object in contact exposure is reduced, and a pattern having excellent linearity is formed. Hereinafter, the photomask according to the above embodiment will be referred to as "photomask according to embodiment 2".

The reason why the photomask according to embodiment 2 exhibits the above-described effect will be described below with reference to fig. 3 and 4. Fig. 3 is a schematic cross-sectional view showing a layer structure of the photomask according to embodiment 2. Fig. 4 is a schematic cross-sectional view showing a layer structure of a photomask according to embodiment 2 in contact with a photosensitive layer.

The photomask 110 shown in fig. 3 includes a transparent support 11, a light shielding layer 21, and a protective layer 31. The transparent support 11 has a 1 st surface 11a and a 2 nd surface 11b. The 1 st surface 11a is covered with the light shielding layer 21 and the protective layer 31. The 2 nd surface 11b is a surface located opposite to the 1 st surface 11 a. The light shielding layer 21 is disposed on a part of the 1 st surface 11a of the transparent support 11. The protective layer 31 is disposed on the 1 st surface 11a of the transparent support 11 and the light shielding layer 21. In other words, the protective layer 31 covers the 1 st surface 11a of the transparent support 11 and the light shielding layer 21. The surface roughness Rz of the protective layer 31 is 0.1 μm to 0.5 μm.

As shown in fig. 4, the photomask 110 is used in contact with the photosensitive layer 210. The surface roughness Rz of the portion of the photomask 110 in contact with the photosensitive layer 210 is adjusted to 0.1 μm to 0.5 μm. The protective layer 31 of the photomask 110 is in contact with the photosensitive layer 210. In fig. 4, a part of the protective layer 31 is not in contact with the photosensitive layer 210 in order to clarify the layer structure. However, the matters shown in fig. 4 do not exclude that all surfaces of the protective layer 31 facing the photosensitive layer 210 are in contact with the photosensitive layer 210. All surfaces of the protective layer 31 facing the photosensitive layer 210 may be in contact with the photosensitive layer 210. In the exposure method of the photosensitive layer 210 using the photomask 110, the photomask 110 is brought into contact with the photosensitive layer 210, and then the photosensitive layer 210 is exposed with the photomask 110 interposed therebetween. The light irradiated from the light source transmits the portion of the transparent support 11 not covered by the light shielding layer 21 (i.e., the light transmitting portion). After exposing the photosensitive layer 210, the photomask 110 is peeled off from the photosensitive layer 210.

As described above, in the exposure method of the photosensitive layer using the photomask according to embodiment 2, the portion (i.e., the protective layer) of the photomask according to embodiment 2 having the surface roughness Rz of 0.1 μm to 0.5 μm is in contact with the object to be contacted (e.g., the photosensitive layer). In the photomask according to embodiment 2, the surface roughness Rz of the portion in contact with the object to be contacted is 0.1 μm to 0.5 μm, whereby the smoothness of the photomask is improved and scattering of light during exposure is suppressed. The smoothness of the photomask is improved, and the adhesiveness of the photomask to a contact object during contact exposure is reduced. Scattering of light during exposure is suppressed, and linearity of the obtained pattern is improved. Therefore, according to an embodiment of the present invention, there is provided a photomask in which adhesiveness to a contact object in contact exposure is reduced, and a pattern having excellent linearity is formed. Hereinafter, the photomask according to embodiment 2 will be described in detail.

[ transparent support ]

The photomask according to embodiment 2 includes a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface. Hereinafter, the transparent support of the photomask according to embodiment 2 will be described in detail.

The transparent support is preferably flat.

The thickness of the transparent support is not limited. The preferred range of the thickness of the transparent support is the same as the preferred range of the thickness of the transparent support described in the above "embodiment 1".

The 1 st surface of the transparent support is a surface on which the light shielding layer and the protective layer are disposed. The 1 st surface of the transparent support faces the light shielding layer and the protective layer.

[ light-shielding layer ]

The photomask according to embodiment 2 includes a light-shielding layer. Hereinafter, a light shielding layer of a photomask according to embodiment 2 will be described in detail.

The light shielding layer is disposed on a part of the 1 st surface of the transparent support. The photosensitive layer can be exposed in a pattern through a photomask by disposing the light shielding layer on a part of the 1 st surface of the transparent support. The position of the light shielding layer may be determined, for example, by the shape of a pattern formed by photolithography.

The composition of the light shielding layer is not limited. Examples of the component of the light-shielding layer include the component of the light-shielding layer described in the above "embodiment 1". The light-shielding layer preferably contains chromium.

The thickness of the light shielding layer is not limited. The thickness of the light shielding layer is preferably thinner than the thickness of the transparent support. The preferable range of the thickness of the light-shielding layer is the same as that described in the above "embodiment 1".

Protective layer

The photomask according to embodiment 2 includes a protective layer. Hereinafter, the protective layer of the photomask according to embodiment 2 will be described in detail.

The protective layer is disposed on the 1 st surface of the transparent support and the light shielding layer. In other words, the protective layer is a layer covering the 1 st surface of the transparent support and the light shielding layer. The protective layer is preferably the outermost layer of the photomask. The protective layer may have a single-layer structure or a multi-layer structure.

The surface roughness Rz of the protective layer is 0.1-0.5 mu m. When the surface roughness Rz of the protective layer is 0.1 μm or more, the smoothness of the photomask is improved, and the adhesiveness of the photomask to a contact object during contact exposure is reduced. By setting the surface roughness Rz of the protective layer to 0.5 μm or less, scattering of light during exposure is suppressed, and the linearity of the obtained pattern is improved. The surface roughness Rz of the light shielding layer is preferably 0.12 μm or more, more preferably 0.15 μm or more, and particularly preferably 0.18 μm or more, from the viewpoint of reducing the adhesiveness of the photomask to a contact object during contact exposure. From the viewpoint of improving the linearity of the pattern, the surface roughness Rz of the light shielding layer is preferably 0.4 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.2 μm or less.

The surface roughness Ra of the protective layer is preferably 5nm to 5Onm. By the surface roughness Ra of the protective layer being 5nm or more, the smoothness of the photomask is improved, and the adhesiveness of the photomask to a contact object during contact exposure is reduced. The surface roughness Ra of the protective layer is 50nm or less, whereby scattering of light during exposure is suppressed and linearity of the obtained pattern is improved. The surface roughness Ra of the protective layer is preferably 10nm or less, more preferably 15nm or more, and particularly preferably 20nm or more, from the viewpoint of reducing the adhesiveness of the photomask to a contact object during contact exposure. From the viewpoint of improving the linearity of the pattern, the surface roughness Ra of the protective layer is preferably 40nm or less, more preferably 35nm or less, and particularly preferably 30nm or less.

The protective layer is preferably a protective layer having small absorption of light in a range from the ultraviolet region to the visible region. If the absorption of light in the ultraviolet region is small, for example, the transmittance of ultraviolet light used in exposure is improved. If the light absorption in the visible region is small, the inspection of the photomask can be performed smoothly. In order to prevent scratches from being generated by mechanical impact, the hardness of the protective layer is preferably 3H or more in terms of pencil hardness. In order to prevent dissolution in solvents (e.g., acetone and methyl ethyl ketone) used as a surface cleaner, the protective layer preferably has solvent resistance. When the protective layer is formed using a composition containing a material for the protective layer, the viscosity of the composition is preferably 1mpa·s to 2mpa·s from the viewpoint of manufacturing the protective layer.

The protective layer preferably contains an organic polymer compound from the viewpoint of solvent resistance. The organic high molecular compound may be a polymer. Examples of the organic polymer compound include an acrylic resin and a urethane resin. The organic polymer compound is preferably at least one selected from the group consisting of acrylic resins and urethane resins. The acrylic resin can be synthesized by a known method. Examples of the material of the acrylic resin include ultraviolet-curable or thermally-curable acrylates and ultraviolet-curable or thermally-curable methacrylates. The material of the acrylic resin may be a monomer or oligomer. The polyurethane resin can be synthesized by a known method. Examples of the material of the urethane resin include polyol and isocyanate. The organic polymer compound preferably contains at least one structural unit selected from urethane acrylates and urethane methacrylates, and more preferably contains structural units derived from urethane acrylates. Urethane acrylate refers to an acrylate containing urethane linkages. Urethane methacrylate refers to a methacrylate containing a urethane bond.

The molecular weight of the organic polymer compound is preferably 5,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more. When the organic high molecular compound has a molecular weight distribution, the molecular weight of the organic high molecular compound is represented by a weight average molecular weight (Mw).

From the viewpoint of low surface energy, the protective layer is preferably a compound containing fluorine atoms. The fluorine atom containing compound may be a polymer. Examples of the fluorine atom-containing compound include (heptadecafluoro-1, 2-tetrahydrodecyl) -1-triethoxysilane. The method for forming the protective layer containing the fluorine atom-containing compound is not limited. Examples of the method for forming the protective layer of the fluorine-containing compound include those described in Japanese patent publication No. 60-40695, japanese patent publication No. 61-48707, japanese patent application laid-open No. 57-46243, japanese patent application laid-open No. 4-1338, japanese patent application laid-open No. 4-73652 and Japanese patent application laid-open No. 11-305420.

The thickness of the protective layer is not limited. The thickness of the protective layer is preferably 1nm or more, more preferably 100nm or more, and particularly preferably 400nm or more from the viewpoint of protection of the light shielding layer. From the viewpoint of resolution, the thickness of the protective layer is preferably 1000nm or less, more preferably 800nm or less, and particularly preferably 600nm or less. The thickness of the protective layer was determined by arithmetically averaging the thickness of the protective layer measured at 10.

[ method of production ]

As a method for manufacturing a photomask according to embodiment 2, for example, a method of roughening the surface of a protective layer using a laminate including a transparent support, a light shielding layer, and the protective layer is given. In one embodiment, the method for manufacturing a photomask preferably includes a 3 rd preparation step and a 3 rd roughening step. In the 3 rd preparation step, a laminate is prepared, the laminate including: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; a light shielding layer disposed on a part of the 1 st surface of the transparent support; and a protective layer disposed on the 1 st surface of the transparent support and the light shielding layer. In the 3 rd roughening step, the laminate is subjected to a blasting treatment to adjust the surface roughness Rz of the protective layer to 0.1 μm to 0.5 μm. The method for manufacturing a photomask more preferably includes a 4 th preparation step and a 4 th roughening step. In the 4 th preparation step, a laminate is prepared, the laminate including: a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface; a light shielding layer disposed on a part of the 1 st surface of the transparent support; and a protective layer disposed on the 1 st surface of the transparent support and the light shielding layer. In the 4 th roughening step, the laminate is subjected to a blasting treatment to adjust the surface roughness Rz of the protective layer to 0.1 μm to 0.5 μm and the surface roughness Ra of the protective layer to 5nm to 50nm. Hereinafter, a method for manufacturing a photomask according to embodiment 2 will be described in detail.

(laminate)

The laminate used in the method for producing a photomask can be produced by a known method for producing a photomask, for example. For example, a material is prepared by (1) comprising a transparent support, a light shielding layer, and a resist in this order; (2) exposure of the resist; (3) Developing the resist, (4) removing the exposed light shielding layer; 5) Removing the resist; and (6) formation of a protective layer, whereby a laminate can be produced.

Examples of the method for forming the protective layer include a method using a composition containing a material for the protective layer. The composition may further contain a solvent. For example, the protective layer can be formed by coating a composition containing a material for the protective layer on the 1 st surface of the transparent support and the light shielding layer. The coating of the composition can be performed using, for example, a spin coater, a slot spin coater, a roll coater, a die coater, or a curtain coater. The applied composition may be dried, as desired. Further, depending on the components of the composition, the composition after application may be heated or the composition after application may be irradiated with ultraviolet rays. Further, as a method for forming the protective layer, for example, a vapor deposition method is given. Examples of the vapor deposition method include a chemical vapor deposition method.

In the method for producing the laminate, a known photomask may be used as a material of the laminate. For example, a laminate can be manufactured by forming a protective layer on a light shielding layer of a known photomask. As a photomask that can be used as a material, for example, a photomask that can be used as a laminate described in the above "embodiment 1" can be cited.

(Sand blasting)

Regarding the blasting treatment, as described in the above "embodiment 1". The blasting is preferably wet blasting.

< exposure method >

The exposure method according to an embodiment of the present invention is an exposure method using the photomask according to an embodiment of the present invention. The exposure method according to an embodiment of the present invention preferably includes: a photomask according to an embodiment of the present invention (hereinafter, sometimes referred to as "5 th preparation step") is prepared; and a step of exposing the photosensitive layer with the photomask in contact with the photosensitive layer with the photomask interposed therebetween (hereinafter, sometimes referred to as "exposure 1 st step"). Hereinafter, an exposure method according to an embodiment of the present invention will be described in detail.

Preparation procedure 5

In the 5 th preparation step, a photomask according to an embodiment of the present invention is prepared. The photomask according to an embodiment of the present invention is as described in the above "photomask". In one embodiment, the photomask is preferably the photomask according to embodiment 1 described in the "photomask" item. In one embodiment, the photomask is preferably the photomask according to embodiment 2 described in the above "photomask".

Exposure procedure 1

In the 1 st exposure step, a photomask is brought into contact with the photosensitive layer, and the photosensitive layer is exposed with the photomask interposed therebetween. The photosensitive layer is exposed through a photomask to form an exposed portion and a non-exposed portion on the photosensitive layer.

[ contact method ]

In the 1 st exposure step, the photomask is brought into contact with the photosensitive layer. The method of bringing the photomask into contact with the photosensitive layer is not limited. For example, the photomask can be brought into contact with the photosensitive layer by relatively moving the photomask with respect to the photosensitive layer. In the 1 st exposure step, the photomask, the photosensitive layer, or both the photomask and the photosensitive layer may be moved.

Specifically, in the 1 st exposure step, a portion of the photomask having a surface roughness Rz of 0.1 μm to 0.5 μm is brought into contact with the photosensitive layer. For example, in the 1 st exposure step using the photomask according to embodiment 1, the light shielding layer of the photomask is brought into contact with the photosensitive layer, and the light shielding layer and the transparent support are sequentially arranged on the photosensitive layer (see fig. 2). In the 1 st exposure step using the photomask according to embodiment 1, both the light-shielding layer and the transparent support may be brought into contact with the photosensitive layer. For example, in the 1 st exposure step using the photomask according to embodiment 2, the protective layer of the photomask is brought into contact with the photosensitive layer, and the protective layer, the light shielding layer, and the transparent support are sequentially disposed on the photosensitive layer (see fig. 4).

[ Exposure Condition ]

In the 1 st exposure step, the photosensitive layer is exposed with a photomask interposed therebetween. The exposure conditions are not limited. In the 1 st exposure step, known exposure conditions can be used.

The light source used in the 1 st exposure step may be a light source that irradiates light (e.g., 365nm or 405 nm) of a wavelength at which the photosensitive layer can be exposed. Examples of the light source include an extra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode: light emitting diode).

The wavelength of the light irradiated in the 1 st exposure step preferably includes a wavelength range of 200nm to 1, 500nm, more preferably a wavelength range of 250nm to 450nm, and particularly preferably a wavelength range of 300nm to 410 nm. Further, the light irradiated in the 1 st exposure step preferably contains light of 365nm or 405nm, and more preferably contains light of 365 nm.

The exposure amount is not limited. The exposure is preferably 5mJ/cm ² ～1,000mJ/cm ² More preferably 10mJ/cm ² ～500mJ/cm ² 。

[ photosensitive layer ]

The kind of the photosensitive layer is not limited. In the 1 st exposure step, a known photosensitive layer can be used. Examples of the photosensitive layer include a positive photosensitive layer and a negative photosensitive layer. Hereinafter, the positive photosensitive layer and the negative photosensitive layer will be described in detail.

(Positive type photosensitive layer)

In the exposure method according to an embodiment of the present invention, a known positive photosensitive layer can be used. The positive photosensitive layer preferably contains a resin and an acid generator. From the viewpoints of sensitivity and resolution, the positive photosensitive layer preferably contains an acid-decomposable resin as a resin and a photoacid generator as an acid generator. From the viewpoints of heat resistance and dimensional stability, the positive photosensitive layer preferably contains an alkali-soluble resin as a resin and a quinone diazide as an acid generator. Hereinafter, the positive photosensitive layer will be described in detail.

Resin-

The positive photosensitive layer preferably contains a resin. Preferable examples of the resin include acid-decomposable resins and alkali-soluble resins. Preferable examples of the acid-decomposable resin include a polymer X containing a structural unit a having an acid group protected with an acid-decomposable group.

The positive photosensitive layer preferably contains, as the acid-decomposable resin, a polymer X containing a structural unit a having an acid group protected by an acid-decomposable group. The positive photosensitive layer may contain other polymers in addition to the polymer X. In the present invention, polymer X and other polymers are collectively referred to as "polymer components". With respect to other polymers, the following will be described. In addition, a compound corresponding to the crosslinking agent, the dispersing agent, or the surfactant is not included in the polymer component.

The acid groups of the polymer X, which are protected by acid-decomposable groups, are subjected to deprotection reaction based on the action of a catalytic amount of an acidic substance (e.g., acid) generated by exposure to light, to become acid groups. The positive photosensitive layer can be dissolved in a developer by converting an acid group protected by an acid-decomposable group into an acid group.

The polymer X is preferably a resin of the addition polymerization type, more preferably a polymer containing a structural unit derived from (meth) acrylic acid or an ester of (meth) acrylic acid. The polymer X may have a structural unit other than a structural unit derived from (meth) acrylic acid or an ester of (meth) acrylic acid (for example, a structural unit derived from a styrene compound and a structural unit derived from a vinyl compound).

The kind of the acid group and the acid-decomposable group is not limited. Preferable examples of the acid group include a carboxyl group and a phenolic hydroxyl group. Examples of the acid-decomposable group include a group which is relatively easily decomposed by an acid (for example, a 1-alkoxyalkyl group, a tetrahydropyranyl group, and an acetal-type acid-decomposable group (for example, a tetrahydrofuranyl group)), and a group which is relatively hardly decomposed by an acid (for example, a tertiary alkyl group such as a tertiary butyl group, and a tertiary alkyloxycarbonyl group such as a tertiary alkyloxycarbonyl group (i.e., a carbonate-type protecting group)). The acid-decomposable group is preferably an acetal-type acid-decomposable group. From the viewpoint of dimensional stability of the obtained pattern, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less.

From the viewpoints of sensitivity and resolution, the structural unit a is preferably a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, or a structural unit represented by the following formula A3.

[ chemical formula 1]

In the formula A1, R ¹¹ R is R ¹² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ¹¹ R is R ¹² At least one of which is alkyl or aryl, R ¹³ Represents alkyl or aryl, R ¹¹ Or R is ¹² And R is R ¹³ Can be linked to form a cyclic ether, R ¹⁴ Represents a hydrogen atom or a methyl group, X ¹ Represents a single bond or a divalent linking group, R ¹⁵ Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R ²¹ R is R ²² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ R is R ²² At least one of which is alkyl or aryl, R ²³ Represents alkyl or aryl, R ²¹ Or R is ²² And R is R ²³ Can be linked to form a cyclic ether, R ²⁴ Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In the formula A3, R ³¹ R is R ³² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³¹ R is R ³² At least one of which is alkyl or aryl, R ³³ Represents alkyl or aryl, R ³¹ Or R is ³² And R is R ³³ Can be linked to form a cyclic ether, R ³⁴ Represents a hydrogen atom or a methyl group, X ⁰ Represents a single bond or a divalent linking group.

The structural unit represented by formula A3 is a structural unit containing a carboxyl group protected by an acetal acid-decomposable group. The polymer X contains the structural unit represented by the formula A3, which is excellent in sensitivity at the time of pattern formation and further excellent in resolution.

In the formula A3, when R ³¹ Or R is ³² When alkyl, R is preferred ³¹ Or R is ³² Is an alkyl group having 1 to 10 carbon atoms. When R is ³¹ Or R is ³² When aryl, R is preferred ³¹ Or R is ³² Is phenyl. R is R ³¹ R is R ³² Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R ³³ The alkyl group or the aryl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

R ³¹ ～R ³³ The alkyl group and the aryl group in (a) may have a substituent.

In the formula A3, R ³¹ Or R is ³² And R is R ³³ May be linked to form a cyclic ether. Preferably R ³¹ Or R is ³² And R is R ³³ To form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, more preferably 5.

In the formula A3, X ⁰ Represents a single bond or an arylene group, preferably a single bond. Arylene groups may have substituents.

In the formula A3, R ³⁴ The hydrogen atom or methyl group is preferably a hydrogen atom from the viewpoint of being able to further lower the glass transition temperature (Tg) of the polymer X. From R, relative to the total amount of the structural units A contained in the polymer X ³⁴ The content of the structural unit represented by the formula A3 which is a hydrogen atom is preferably 20 mass% or more. In addition, R is ³⁴ The content (mass basis) of the structural unit represented by the formula A3 as a hydrogen atom can be determined from ¹³ C-Nuclear magnetic resonance Spectrometry (NMR) determination the intensity ratio of the peak intensities calculated by conventional methods.

For preferable embodiments of formulas A1 to A3, reference can be made to paragraphs 0044 to 0058 of international publication No. 2018/179640.

In the formulae A1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, still more preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group, from the viewpoint of sensitivity.

The polymer X may contain one or more than two structural units A alone.

The content of the structural unit a in the polymer X is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass, relative to the total mass of the polymer components. If the content of the structural unit a in the polymer X is within the above range, the resolution is further improved. When the polymer X contains two or more structural units a, the content of the structural units a represents the total content of the two or more structural units a. The content (mass basis) of the structural unit A can be determined by ¹³ C-NMR measurement the intensity ratio of the peak intensities calculated by the conventional method was calculated.

The polymer X may contain a structural unit B having an acid group. The structural unit B has an acid group not protected by an acid-decomposable group, i.e., has an acid group structural unit having no protecting group. The polymer X contains the structural unit B, so that the sensitivity at the time of pattern formation is improved, and the photosensitive layer is easily dissolved in an alkaline developer during development after exposure, thereby enabling a reduction in development time. The acid group in the structural unit B is a proton dissociative group having a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. The pKa of the acid group is preferably-5 or more. Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, more preferably a carboxyl group.

The polymer X may contain one or more than two structural units B alone.

The content of the structural unit B in the polymer X is preferably 0.01 to 20% by mass based on the total mass of the polymer componentsThe content is more preferably 0.01 to 10% by mass, particularly preferably 0.1 to 5% by mass. When the content of the structural unit B in the polymer X is within the above range, the resolution becomes better. When the polymer X contains two or more structural units B, the content of the structural units B represents the total content of the two or more structural units B. The content (mass basis) of the structural unit B can be determined by ¹³ C-NMR measurement the intensity ratio of the peak intensities calculated by the conventional method was calculated.

The polymer X may contain a structural unit C other than the structural unit A and the structural unit B. For example, by adjusting the type and content of the structural unit C, various characteristics of the polymer X can be adjusted. In particular, by containing the structural unit C in the polymer X, tg, acid value, hydrophilicity and hydrophobicity of the polymer X can be easily adjusted.

Examples of the monomer forming the structural unit C include styrene-based monomers, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, dicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene-based compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, and monomers containing a group having an aliphatic cyclic skeleton. Examples of the monomer forming the structural unit C include compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623.

Examples of the structural unit C include structural units obtained by polymerizing styrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate.

From the viewpoint of resolution, the structural unit C preferably contains a structural unit having an alkaline group. Examples of the basic group include a group having a nitrogen atom. Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic group. The basic group is preferably an aliphatic amino group. Examples of the aliphatic amino group include a primary amino group, a secondary amino group, and a tertiary amino group. From the viewpoint of resolution, the aliphatic amino group is preferably a secondary amino group or a tertiary amino group.

As a monomer forming a structural unit having a basic group, examples thereof include 1,2, 6-pentamethyl-4-piperidine methacrylate, 2- (dimethylamino) ethyl methacrylate, 2, 6-tetramethyl-4-piperidine acrylate, 2, 6-tetramethyl-4-piperidine methacrylate, 2, 6-tetramethyl-4-piperidine acrylate 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl ] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1, 2, 4-triazole. Among the above monomers, 1,2, 6-pentamethyl-4-piperidyl methacrylate is preferred.

From the viewpoint of improving the electrical characteristics of the photosensitive layer, the structural unit C is preferably a structural unit having an aromatic ring or an aliphatic ring-type skeleton structural unit. Examples of the monomer forming the structural unit include styrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among the above monomers, cyclohexyl (meth) acrylate may be preferably used.

The monomer forming the structural unit C is preferably an alkyl (meth) acrylate, more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms, from the viewpoint of adhesion of the photosensitive layer to other layers. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The polymer X may contain one or more than two structural units C alone.

The content of the structural unit C in the polymer X is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less, relative to the total mass of the polymer components. The content of the structural unit C in the polymer X is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the polymer components. When the content of the structural unit C is within the above range, the resolution and adhesion are further improved. When the polymer X contains two or more structural units C, the content of the structural units C represents the total content of the two or more structural units C.

Preferred polymers X are shown below. However, the polymer X is not limited to the examples shown below. The ratio of the structural units and the weight average molecular weight of the polymer X shown below can be appropriately selected in order to obtain preferable physical properties.

[ chemical formula 2]

The glass transition temperature (Tg) of the polymer X is preferably 90℃or lower, more preferably 20℃to 60℃and particularly preferably 30℃to 50 ℃. For example, when a photosensitive transfer material is used to prepare a photosensitive layer, the transferability is improved by the glass transition temperature of the polymer X being 90 ℃ or less. For example, according to the Tg of the homopolymer of the structural unit and the mass ratio of the structural unit contained in the target polymer X, the Tg of the target polymer X can be controlled based on the FOX formula. Further, by adjusting the weight average molecular weight of the polymer X, the Tg of the polymer X can also be adjusted.

Hereinafter, a copolymer containing the 1 st structural unit and the 2 nd structural unit will be described as an example of the FOX formula. When Tg of the homopolymer of the 1 st structural unit is Tg1, the mass fraction of the 1 st structural unit in the copolymer is W1, tg of the homopolymer of the 2 nd structural unit is Tg2, and the mass fraction of the 2 nd structural unit in the copolymer is W2, tg0 (unit: K) of the copolymer containing the 1 st structural unit and the 2 nd structural unit can be estimated according to the following formula. By adjusting the type and mass fraction of each structural unit contained in the copolymer using the FOX formula, a copolymer having a desired Tg can be obtained.

FOX formula: 1/Tg 0= (W1/Tg 1) + (W2/Tg 2)

From the viewpoint of resolution, the acid value of the polymer X is preferably 0mgKOH/g to 50mgKOH/g, more preferably 0mgKOH/g to 20mgKOH/g, and particularly preferably 0mgKOH/g to 10mgKOH/g. The acid value of the polymer X is preferably 10mgKOH/g or less, more preferably 3mgKOH/g or less, from the viewpoints of storage stability and adhesion of the photosensitive layer to other layers.

In the present invention, the acid value of the polymer means the mass of potassium hydroxide required for neutralizing the acid component per 1g of the measurement sample. Specifically, using a potential difference titration apparatus (for example, KYOTO ELECTRONICS MANUFACTURING co., ltd. Manufactured AT-510), a solution obtained by dissolving a measurement sample in a mixed solvent of tetrahydrofuran/water=9/1 (volume ratio) was subjected to neutralization titration with a 0.1mol/L aqueous sodium hydroxide solution. The measurement was performed at 25 ℃. The acid value was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: the amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration

f: titration amount of 0.1mol/L sodium hydroxide aqueous solution

w: measuring the mass (g) of the sample (conversion of solid content)

The molecular weight of the polymer X is preferably 60,000 or less in terms of polystyrene. When the weight average molecular weight of the polymer X is 60,000 or less, for example, when a photosensitive transfer material containing a photosensitive layer is used to prepare a photosensitive layer, transfer at a low temperature (for example, 130 ℃ or less) can be achieved. The weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000. The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

In the present invention, the weight average molecular weight of the polymer is determined by Gel Permeation Chromatography (GPC). In the measurement of the weight average molecular weight by Gel Permeation Chromatography (GPC), HLC (registered trademark) -8220GPC (TOSOH CORPORATION) was used as a measurement device, a column in which TSKgel (registered trademark) Super HZM-M (4.6 mmid× 15cm,TOSOH CORPORATION), super HZ4000 (4.6 mmid× 15cm,TOSOH CORPORATION), super HZ3000 (4.6 mmid× 15cm,TOSOH CORPORATION), and Super HZ2000 (4.6 mmid× 15cm,TOSOH CORPORATION) were connected in series was used as a column, and THF (tetrahydrofuran) was used as an eluent. The measurement conditions were set to 0.2 mass% for the sample concentration, 0.35 mL/min for the flow rate, 10. Mu.L for the sample injection amount, and 40℃for the measurement temperature. As the detector, a differential Refractive Index (RI) detector is used. The calibration curve can be made using a "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: any of the 7 samples "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" were prepared.

The positive photosensitive layer may contain one or two or more kinds of polymers X alone.

The content of the polymer X in the positive photosensitive layer is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, based on the total mass of the positive photosensitive layer.

The method for producing the polymer X is not limited. For example, the polymer X can be produced by polymerizing a monomer using a polymerization initiator in an organic solvent containing a monomer for forming the structural unit a and further containing a monomer for forming the structural unit B and a monomer for forming the structural unit C as needed. The polymer X can also be produced by a so-called polymer reaction.

The positive photosensitive layer may further contain, as another polymer, a polymer that does not contain a structural unit having an acid group protected by an acid-decomposable group, in addition to the polymer X. Examples of the other polymer include polyhydroxystyrene. Examples of the commercial products of the other polymers include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA P and SMA 3840F (manufactured by Sartomer Company, inc. above), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (manufactured by TOAGOSEI CO., LTD. Above) and Joncryl 690, joncryl 678, joncryl 67 and Joncryl 586 (manufactured by BASF corporation, above).

The positive photosensitive layer may contain one or two or more other polymers.

When the positive photosensitive layer contains another polymer, the content of the other polymer is preferably 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 20 mass% or less, relative to the total mass of the polymer components.

The content of the polymer component in the positive photosensitive layer is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, based on the total mass of the positive photosensitive layer.

The positive photosensitive layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide.

Examples of the alkali-soluble resin include resins having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or a side chain. Examples of the alkali-soluble resin include polyamide resins, polyhydroxystyrenes, polyhydroxystyrene derivatives, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoates, carboxyl group-containing (meth) acrylic resins, and novolak resins. Preferable alkali-soluble resins include, for example, polycondensates of m-/p-cresol and formaldehyde and polycondensates of phenol, cresol and formaldehyde.

The alkali-soluble resin may have a phenolic hydroxyl group (-Ar-OH) and a carboxyl group (-CO) ₂ H) Sulfo (-SO) ₃ H) Phosphate group (-OPO) ₃ H) Sulfonamide (-SO) ₂ NH-R) or substituted sulfonamide-based acid groups (e.g., reactive imide groups, -SO ₂ NHCOR、-SO ₂ NHSO ₂ R and-CONHSO ₂ R). Here, ar represents a 2-valent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

The novolak resin is obtained, for example, by condensing a phenol compound and an aldehyde compound in the presence of an acid catalyst. Examples of the phenol compound include o-, m-or p-cresol, 2,5-, 3, 5-or 3, 4-xylenol (xylenol), 2,3, 5-trimethylphenol, 2-t-butyl-5-methylphenol and t-butylhydroquinone. Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde and glyoxal) and aromatic aldehydes (for example, benzaldehyde and Liu Quan (silicalyaldehyde)), examples of the acid catalyst include inorganic acids (for example, hydrochloric acid, sulfuric acid and phosphoric acid), organic acids (for example, oxalic acid, acetic acid and p-toluenesulfonic acid) and divalent metal salts (for example, zinc acetate), and the condensation reaction can be carried out according to a conventional method.

From the viewpoint of pattern formability, the alkali-soluble resin preferably has a weight average molecular weight of 5.0X10 ² ～2.0×10 ⁵ . From the viewpoint of pattern formability, the number average molecular weight of the alkali-soluble resin is preferably 2.0X10 ² ～1.0×10 ⁵ 。

The positive photosensitive layer may contain one kind or two or more kinds of alkali-soluble resins alone.

The positive photosensitive layer may contain a polycondensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent (hereinafter referred to as "1 st polycondensate"). Examples of the 1 st polycondensate include a polycondensate of tert-butylphenol and formaldehyde and a polycondensate of octylphenol and formaldehyde described in U.S. Pat. No. 4123279. The positive photosensitive layer may contain a polycondensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent (hereinafter referred to as "the 2 nd polycondensate"). Examples of the 2 nd polycondensate include t-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in the specification of U.S. Pat. No. 4123279.

The content of the alkali-soluble resin is preferably 30 to 99.9 mass%, more preferably 40 to 99.5 mass%, and particularly preferably 70 to 99 mass%, relative to the total mass of the positive photosensitive layer.

Acid generator-

The positive photosensitive layer preferably contains an acid generator, and more preferably contains a photoacid generator. Acid generators are compounds that generate acid by light or heat. Photoacid generators are compounds that generate acid by irradiation with active light rays (e.g., ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams). The photoacid generator is preferably a compound that generates an acid in response to an active light having a wavelength of 300nm or more (preferably an active light having a wavelength of 300nm to 450 nm). The photoacid generator that does not directly react with the active light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as the photoacid generator is a compound that reacts with the sensitizer to generate an acid in response to the active light having a wavelength of 300nm or more.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit value of pKa is not limited. The pKa is, for example, preferably-10.0 or more.

The photoacid generator is preferably a compound that generates an acid by containing light having a wavelength of 365nm or 405nm, and more preferably a compound that generates an acid by containing light having a wavelength of 365 nm.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator. Examples of the ionic photoacid generator include onium salt compounds (for example, diaryliodonium salts and triarylsulfonium salts) and quaternary ammonium salts. Among the above-mentioned ionic photoacid generators, the ionic photoacid generator is preferably an onium salt compound, more preferably a triarylsulfonium salt or a diaryliodonium salt. As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A2014-85643 can also be preferably used. Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among the above nonionic photoacid generators, the oxime sulfonate compound is preferable from the viewpoints of sensitivity, resolution and adhesion. Examples of the trichloromethyl-s-triazine compound, diazomethane compound and imide sulfonate compound include those described in paragraphs 0083 to 0088 of JP-A2011-221494. As the oxime sulfonate compound, for example, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be preferably used.

From the viewpoints of sensitivity and resolution, the photoacid generator is preferably at least one selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably an oxime sulfonate compound.

Examples of the photoacid generator include photoacid generators having the following structures.

[ chemical formula 3]

From the viewpoints of heat resistance and dimensional stability, the positive photosensitive layer preferably contains quinone diazide as an acid generator (preferably, photoacid generator). Quinone diazide can be synthesized, for example, by condensation reaction of a compound having a phenolic hydroxyl group with quinone diazide sulfonyl halide in the presence of a dehydrohalogenating agent.

Examples of the quinone diazide include 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 1, 2-naphthoquinone diazide-6-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-6-sulfonate, sulfonate of other quinone diazide derivatives, 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 1, 2-naphthoquinone diazide-6-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, 2, 1-naphthoquinone diazide-5-sulfonyl chloride and 2, 1-naphthoquinone diazide-6-sulfonyl chloride.

The positive photosensitive layer may contain one kind or two or more kinds of acid generators.

From the viewpoints of the taper angle of the obtained pattern, the dimensional stability, sensitivity, and resolution of the obtained pattern, the content of the acid generator in the positive photosensitive layer is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, still more preferably 2.5 mass% or more, particularly preferably 3.0 mass% to 10 mass%, and most preferably 3.5 mass% to 10.0 mass% relative to the total mass of the positive photosensitive layer.

Other ingredients-

The positive photosensitive layer may contain other components than the above components. Examples of the other component include solvents, plasticizers, sensitizers, heterocyclic compounds, alkoxysilane compounds, basic compounds, rust inhibitors, and surfactants. Examples of plasticizers, sensitizers, heterocyclic compounds and alkoxysilane compounds include those described in paragraphs 0097 to 0119 of International publication No. 2018/179640.

The positive photosensitive layer preferably contains an alkaline compound. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of the basic compound include those described in paragraphs 0204 to 0207 of Japanese patent application laid-open No. 2011-221494. As a preferred basic compound, N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (CMTU) is mentioned. As a commercial product of cmts, cmts manufactured by Toyo Kasei Kogyo co.

The basic compound is preferably a benzotriazole compound. The benzotriazole compound is not limited as long as it is a compound having a benzotriazole skeleton. Examples of the benzotriazole compound include 1,2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H-benzole, 1-acetyl-1H-benzole, 1-aminobenzole, 9- (1H-benzole-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzole, 1- (2-pyridyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1 ' -hydroxyethyl) benzotriazole, 1- (2 ' -hydroxyethyl) benzotriazole, 1-propylbenzotriazole, 1- (1 ' -hydroxypropyl) benzotriazole, 1- (2 ' -hydroxypropyl) benzotriazole, 1- (3 ' -hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzole, 5-methyl-1H-benzole-e-triazole, benzotriazole-5-carboxylic acid methyl-5-benzole ester, benzotriazole-5-carboxylic acid tert-butyl ester, 1-benzole-5-carboxylic acid, and 1-ethylbenzotriazole-1-H-carboxylic acid tert-butyl ester, 2-methyl-2H-benzotriazole and 2-ethyl-2H-benzotriazole.

The positive photosensitive layer may contain one kind or two or more kinds of alkaline compounds.

The content of the basic compound is preferably 0.001 to 5 mass%, more preferably 0.005 to 3 mass%, based on the total mass of the positive photosensitive layer.

From the viewpoint of thickness uniformity, the positive photosensitive layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants.

Examples of the commercial products of the surfactant include MEGAFACE F-552 and MEGAFACE F-554 (manufactured by DIC Corporation).

Examples of the surfactant include surfactants described in paragraphs 0120 to 0125 of Japanese patent application laid-open No. 2018/179640, paragraph 0017 of Japanese patent application laid-open No. 4502784, and paragraphs 0060 to 0071 of Japanese patent application laid-open No. 2009-237362.

In recent years, it has been revealed that a compound having a linear perfluoroalkyl group having 7 or more carbon atoms has high toxicity and ecological accumulation (bioaccumulation potential). Therefore, the use of PFOA (perfluorooctanoic acid) and PFOS (perfluorooctane sulfonate) has been limited. Therefore, surfactants using PFOA and PFOS as alternative materials are preferably used.

The positive photosensitive layer may contain one or two or more surfactants alone.

The content of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, based on the total mass of the positive photosensitive layer.

The positive photosensitive layer may contain metal oxide particles, an antioxidant, a dispersant, an acid-proliferation agent, a development accelerator, conductive fibers, a colorant, a thermal radical polymerization initiator, a thermal acid generator, an ultraviolet absorber, a thickener, a crosslinking agent, or an anti-settling agent as other components. A preferable embodiment of the above-mentioned components is described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643. The contents of the above publications are incorporated by reference into the present specification.

Thickness of positive photosensitive layer

The thickness of the positive photosensitive layer is not limited. The thickness of the positive photosensitive layer is preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, and particularly preferably 30 μm or more. The thickness of the positive photosensitive layer is preferably 100 μm or less.

Method for forming positive photosensitive layer

The positive photosensitive layer can be formed, for example, by preparing a composition containing a component for forming the positive photosensitive layer and a solvent, then applying the composition to an object to be coated (for example, a substrate), and drying the composition.

As the solvent, a known solvent can be used. Examples of the solvent include those described in paragraphs 0092 to 0094 of International publication No. 2018/179640. As the solvent, a solvent having a vapor pressure of 1kPa or more and 16kPa or less at 20℃as described in paragraph 0014 of Japanese patent application laid-open No. 2018-177889 can be preferably used. As the solvent, the solvents described in the following "negative photosensitive layer" item can also be used.

The composition may contain a single solvent or two or more solvents.

The content of the solvent in the composition is preferably 50 to 1 part by mass, 900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the composition.

The method of preparing the composition is not limited. For example, the composition can be prepared by mixing solutions obtained by dissolving the components in the solvent in a predetermined ratio. The composition may be filtered, for example, using a filter having a pore size of 0.2 μm to 30 μm.

The coating method of the composition is not limited. Examples of the method for applying the composition include a slit coating method, a spin coating method, a curtain coating method, and an inkjet coating method.

The positive photosensitive layer in contact with the photomask may be a positive photosensitive layer transferred onto a transfer target (e.g., a substrate) using a photosensitive transfer material (hereinafter referred to as "transfer material" in this paragraph). As the transfer material, a known transfer material can be used. Examples of the transfer material include a temporary support and a positive photosensitive layer. For example, a transfer material including a temporary support and a positive photosensitive layer can be produced by preparing a composition containing a component for forming a positive photosensitive layer and a solvent, applying the composition to the temporary support, and drying the composition. Next, a method of using the transfer material will be described. For example, in a method of transferring a positive photosensitive layer to a transfer target using a transfer material including a temporary support and a positive photosensitive layer, the positive photosensitive layer of the transfer material is attached to the transfer target, and after the positive photosensitive layer of the transfer material is brought into contact with the transfer target, the temporary support is peeled off from the positive photosensitive layer, whereby the positive photosensitive layer can be disposed on the transfer target. As a method of bonding the transfer material to the transfer target, a known method can be used. The transfer material is preferably bonded to the transfer target under pressure and heat. The transfer material and the transfer target can be bonded using, for example, a laminator, a vacuum laminator, or an automatic cutting laminator that can further improve productivity.

(negative photosensitive layer)

Next, the negative photosensitive layer will be described. In the exposure method according to an embodiment of the present invention, a known negative photosensitive layer can be used.

In one embodiment, the negative photosensitive layer preferably contains a polymer a, a polymerizable compound B, and a photopolymerization initiator. In one embodiment, the negative photosensitive layer more preferably contains 10 to 90 mass% of the polymer a, 5 to 70 mass% of the polymerizable compound B, and 0.01 to 20 mass% of the photopolymerization initiator, based on the total mass of the negative photosensitive layer.

In one embodiment, the negative photosensitive layer preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.

In one embodiment, the negative photosensitive layer preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photoacid generator from the viewpoints of hardenability and developability.

In one embodiment, the negative photosensitive layer preferably contains a multifunctional epoxy resin, a hydroxyl group-containing compound, and a photo-cationic polymerization initiator from the viewpoints of strength and durability of the obtained resin pattern as a permanent film.

Hereinafter, the negative photosensitive layer will be described in detail.

Polymer A-

The negative photosensitive layer preferably contains a polymer a. Polymer a is preferably an alkali soluble polymer. The alkali-soluble polymer contains a polymer that is easily dissolved in an alkali substance. In the present invention, "alkali-soluble" means that the solubility of 100g of a 1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.

The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and particularly preferably less than 190mgKOH/g, from the viewpoint of improving the resolution by suppressing swelling of the negative photosensitive layer due to the developer. The lower limit of the acid value is not limited. The acid value of the polymer A is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, particularly preferably 170mgKOH/g or more, from the viewpoint of more excellent developability. The acid value of the polymer a can be adjusted, for example, according to the type of the structural unit constituting the polymer a and the content of the structural unit having an acid group. The acid value of the polymer a was measured by the method described in the above item "positive photosensitive resin layer".

The weight average molecular weight (Mw) of polymer A is preferably 5,000 ～ 500,000. From the viewpoint of improving the resolution and the developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight of the polymer a is 100,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developing aggregate, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight of the polymer a is 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more.

The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. Dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing the line width thickening and the deterioration of resolution at the time of the focus position deviation at the time of exposure, the polymer a preferably contains a structural unit having an aromatic hydrocarbon group, and more preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

The content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of the polymer a. The upper limit of the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is not limited. The content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer a is preferably 95 mass% or less, more preferably 85 mass% or less, relative to the total mass of the polymer a. When the negative photosensitive layer contains a plurality of polymers a, the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, a styrene dimer, and a styrene trimer). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.

Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group (for example, benzyl (meth) acrylate and chlorobenzyl (meth) acrylate) and vinyl monomers having a benzyl group (for example, vinylbenzyl chloride and vinylbenzyl alcohol). The monomer having a benzyl group is preferably benzyl (meth) acrylate.

In one embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer a is a structural unit derived from benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate monomer in the polymer a is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, relative to the total mass of the polymer a.

In one embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer a is a structural unit derived from styrene, the content of the structural unit derived from styrene in the polymer a is preferably 20 to 55 mass%, more preferably 25 to 45 mass%, still more preferably 30 to 40 mass%, and particularly preferably 30 to 35 mass% with respect to the total mass of the polymer a.

In one embodiment, the polymer a having a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a copolymer obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one selected from a first monomer described below and a second monomer described below. The copolymer contains a structural unit derived from a monomer having an aromatic hydrocarbon group and at least one selected from the group consisting of a structural unit derived from a first monomer and a structural unit derived from a second monomer.

The polymer a may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. The polymer a having no structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing at least one type of first monomer (except for a monomer having an aromatic hydrocarbon group) described later, more preferably a copolymer obtained by polymerizing at least one type of first monomer (except for a monomer having an aromatic hydrocarbon group) described later and at least one type of second monomer (except for a monomer having an aromatic hydrocarbon group) described later.

In one embodiment, the polymer a is preferably a polymer obtained by polymerizing at least one first monomer described later, and more preferably a copolymer obtained by polymerizing at least one first monomer described later and at least one second monomer described later. The copolymer contains structural units derived from a first monomer and structural units derived from a second monomer.

The first monomer is a monomer having a carboxyl group and a polymerizable unsaturated group in the molecule. The first monomer may be a monomer having no aromatic hydrocarbon group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester. The first monomer is preferably (meth) acrylic acid.

The content of the structural unit derived from the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, relative to the total mass of the polymer a.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. The second monomer may be a monomer having no aromatic hydrocarbon group in the molecule. Examples of the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile.

Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. The (meth) acrylate compound may contain an alicyclic alkyl group, a linear alkyl group, or a branched alkyl group.

In the present invention, "(meth) acrylonitrile" contains acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

Examples of the ester compound of vinyl alcohol include vinyl acetate.

The second monomer is preferably at least one selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate, and more preferably methyl (meth) acrylate.

The content of the structural unit derived from the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 45% by mass, relative to the total mass of the polymer a.

From the viewpoint of suppressing the line width thickening and the deterioration of resolution at the time of the focus position deviation at the time of exposure, the polymer a preferably contains at least one selected from the group consisting of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene. For example, the polymer a is preferably at least one selected from the group consisting of a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate and a structural unit derived from styrene, and a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate and a structural unit derived from styrene.

In one embodiment, the polymer a preferably contains 25 to 60 mass% of a structural unit derived from a monomer having an aromatic hydrocarbon group, 20 to 55 mass% of a structural unit derived from a first monomer, and 20 to 55 mass% of a structural unit derived from a second monomer. More preferably, the polymer a contains 25 to 40 mass% of a structural unit derived from a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of a structural unit derived from a first monomer, and 30 to 45 mass% of a structural unit derived from a second monomer.

In one embodiment, the polymer a preferably contains 70 to 90 mass% of the structural unit derived from the monomer having an aromatic hydrocarbon group and 10 to 25 mass% of the structural unit derived from the first monomer.

The polymer a may have a branched structure or an alicyclic structure in a side chain. For example, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure on the side chain or a monomer containing a group having an alicyclic structure on the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.

Examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Among the above, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. For example, (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are mentioned. Examples of the monomer having a group having an alicyclic structure in a side chain include (bicyclo [2.2.1] heptyl-2) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methylindenyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, octahydro-4, 7-methylindenyl (meth) acrylate, and octahydro-1-menthyl (meth) acrylate Tricyclodecane (meth) acrylate, 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, camphene (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate and cyclohexyl (meth) acrylate. Among the above, cyclohexyl (meth) acrylate, camphene (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate and tricyclodecane (meth) acrylate are preferable, and cyclohexyl (meth) acrylate, camphene (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate and tricyclodecane (meth) acrylate are more preferable.

The glass transition temperature (Tg) of the polymer A is preferably from 30℃to 135 ℃. In the negative photosensitive layer, the Tg of the polymer a is 135 ℃ or lower, whereby the thickness of the line width and the resolution deterioration at the time of focus position deviation at the time of exposure can be suppressed. From the above viewpoints, the Tg of the polymer A is preferably 130℃or lower, more preferably 120℃or lower, particularly preferably 110℃or lower. Further, from the viewpoint of improving the edge melting resistance, the Tg of the polymer a is preferably 30 ℃ or higher. From the above viewpoints, the Tg of the polymer A is 40℃or higher, more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.

The polymer A may be a commercially available product or a synthetic product. The polymer a is preferably synthesized, for example, by adding an appropriate amount of a radical polymerization initiator (e.g., benzoyl peroxide or azoisobutyronitrile) to a solution obtained by diluting the above-mentioned at least one monomer with a solvent (e.g., acetone, methyl ethyl ketone, or isopropyl alcohol), followed by heating and stirring. In some cases, synthesis is performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to the solution containing the polymer a to adjust the concentration of the polymer a to a desired concentration with respect to the solution containing the polymer a. As the synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The negative photosensitive layer preferably contains an alkali-soluble polymer. The acid value of the alkali-soluble polymer is preferably 60mgKOH/g or more, for example, from the viewpoint of developability.

For example, from the viewpoint of easy formation of a firm film by crosslinking with the crosslinking component by heating, the alkali-soluble polymer is preferably a resin having a carboxyl group (so-called carboxyl group-containing resin) having an acid value of 60mgKOH/g or more, more preferably a (meth) acrylic resin having a carboxyl group (so-called carboxyl group-containing (meth) acrylic resin) having an acid value of 60mgKOH/g or more. The content of the structural unit derived from the (meth) acrylic compound in the acrylic resin is preferably 30 mass% or more, more preferably 50 mass% or more, relative to the total mass of the acrylic resin. If the alkali-soluble polymer is a resin having a carboxyl group, for example, crosslinking with a thermally crosslinkable compound such as a blocked isocyanate compound can increase the three-dimensional crosslinking density. Further, if the carboxyl group of the resin having a carboxyl group is dehydrated and rendered hydrophobic, the wet heat resistance can be improved. Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-95716 and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589.

The alkali-soluble polymer is preferably an acrylic resin or a styrene-acrylic copolymer, more preferably a styrene-acrylic copolymer, from the viewpoints of development residue inhibition, moisture permeability of the resulting cured film, and adhesiveness of the resulting uncured film. In the present invention, the "styrene-acrylic acid copolymer" means a resin containing a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound. The total content of the structural units derived from the styrene compound and the structural units derived from the (meth) acrylic compound is preferably 30 mass% or more, more preferably 50 mass% or more, based on the total mass of the styrene-acrylic copolymer. The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 5% by mass or more and 80% by mass or less, relative to the total mass of the styrene-acrylic copolymer. The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more and 95% by mass or less, relative to the total mass of the styrene-acrylic copolymer. Examples of the (meth) acrylic compound include a (meth) acrylic ester compound, (meth) acrylic acid, (meth) acrylamide compound, and (meth) acrylonitrile. The (meth) acrylic compound is preferably at least one selected from the group consisting of a (meth) acrylic acid ester compound and (meth) acrylic acid.

The negative photosensitive layer may contain one kind or two or more kinds of alkali-soluble polymers.

The content of the alkali-soluble polymer is preferably 10 to 90 mass%, more preferably 30 to 70 mass%, and particularly preferably 40 to 60 mass%, relative to the total mass of the negative photosensitive layer. From the viewpoint of controlling the development time, the content of the alkali-soluble polymer relative to the negative photosensitive layer is preferably 90 mass% or less. From the viewpoint of improving the edge melting resistance, the content of the alkali-soluble polymer relative to the negative photosensitive layer is preferably 10 mass% or more.

When the negative photosensitive layer contains two or more alkali-soluble polymers, the negative photosensitive layer preferably contains two or more alkali-soluble polymers having a structural unit derived from a monomer having an aromatic hydrocarbon group, or an alkali-soluble polymer having a structural unit derived from a monomer having an aromatic hydrocarbon group and an alkali-soluble polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content of the alkali-soluble polymer having a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the alkali-soluble polymer.

Polymerizable Compound B-

The negative photosensitive layer preferably contains a polymerizable compound B. The polymerizable compound B is a compound different from the polymer a.

In the present invention, the "polymerizable compound" means a compound having a bond or a polymerizable group which participates in a polymerization reaction and polymerized by the action of a polymerization initiator described later. Examples of the bond involved in the polymerization reaction include an ethylenic unsaturated bond. Examples of the polymerizable group include a group containing an ethylenic unsaturated bond (for example, a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group) and a cationically polymerizable group (for example, an epoxy group and an oxetanyl group). The polymerizable group is preferably a group containing an ethylenic unsaturated bond (hereinafter, sometimes referred to as "ethylenic unsaturated group"), and more preferably an acryl group or a methacryl group.

From the viewpoint of more excellent photosensitivity of the negative photosensitive layer, the polymerizable compound B is preferably a compound having an ethylenic unsaturated bond, more preferably a compound having 1 or more ethylenic unsaturated groups in one molecule (i.e., an ethylenic unsaturated compound), and particularly preferably a compound having 2 or more ethylenic unsaturated groups in one molecule (i.e., a polyfunctional ethylenic unsaturated compound). The number of ethylenic unsaturated groups contained in the ethylenic unsaturated compound of one molecule is preferably 6 or less, more preferably 3 or less, and particularly preferably 2 or less, from the viewpoint of more excellent resolution and releasability. From the viewpoints of hardenability and strength and durability as a permanent film, the polymerizable compound B is preferably a compound having 3 or more ethylenically unsaturated groups in one molecule, and more preferably a compound having 5 or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated compound is preferably a (meth) acrylate compound having 1 or more (meth) acryloyl groups in one molecule.

From the viewpoint of more excellent balance of photosensitivity, resolution and releasability in the negative photosensitive layer, the polymerizable compound B preferably contains at least one selected from the group consisting of a compound having 2 ethylenic unsaturated groups in one molecule (i.e., a 2-functional ethylenic unsaturated compound) and a compound having 3 ethylenic unsaturated groups in one molecule (i.e., a 3-functional ethylenic unsaturated compound), and more preferably contains a compound having 2 ethylenic unsaturated groups in one molecule.

From the viewpoints of strength and dimensional stability after curing, the polymerizable compound B is preferably an ethylenically unsaturated compound having an aliphatic cyclic skeleton, more preferably a di (meth) acrylate compound having an aliphatic cyclic skeleton, and particularly preferably a di (meth) acrylate compound having a dicyclopentyl structure or a dicyclopentenyl structure.

From the viewpoints of strength and dimensional stability after curing, the polymerizable compound B is preferably an ethylenically unsaturated compound having a dicyclopentyl structure or a dicyclopentenyl structure.

In the negative photosensitive layer, the ratio of the content of the 2-functional ethylenically unsaturated compound to the content of the polymerizable compound B is preferably 40% by mass or more, more preferably 60% by mass or more, and particularly preferably more than 70% by mass, from the viewpoint of excellent releasability of the negative photosensitive layer. The upper limit of the content of the 2-functional ethylenically unsaturated compound relative to the content of the polymerizable compound B is not limited, and may be 100 mass%. That is, all of the polymerizable compounds B contained in the negative photosensitive layer may be 2-functional ethylenically unsaturated compounds.

The negative photosensitive layer preferably contains a polymerizable compound B1 having 1 or more aromatic rings and 2 ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is one of the polymerizable compounds B.

Examples of the aromatic ring in the polymerizable compound B1 include an aromatic hydrocarbon ring (for example, benzene ring, naphthalene ring, and anthracene ring), an aromatic heterocyclic ring (for example, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring), and a condensed ring thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The aromatic ring may further have a substituent.

From the viewpoint of improving the resolution by suppressing swelling of the negative photosensitive layer due to the developer, the polymerizable compound B1 preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (i.e., 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (i.e., 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (i.e., 2-bis (4-hydroxyphenyl) butane). The bisphenol structure is preferably a bisphenol a structure.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly bonded to the bisphenol structure. Each polymerizable group may be bonded to the bisphenol structure via 1 or more alkylene oxide groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkylene oxide groups added to the bisphenol structure is not limited, but is preferably 4 to 16, more preferably 6 to 14, per molecule.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A2016-224162. The contents of the above publications are incorporated by reference into the present specification.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane.

Examples of the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecaethoxy tetrapropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical co), and manufactured by ltd.10-b.10, and also, the use of the same.

The polymerizable compound B1 may be, for example, a compound represented by the following general formula (I).

[ chemical formula 4]

In the general formula (I), R ₁ R is R ₂ Each independently represents a hydrogen atom or a methyl group, A represents C ₂ H ₄ B represents C ₃ H ₆ ，n ₁ N is as follows ₃ Each independently represents an integer of 1 to 39, n ₁ +n ₃ Is an integer of 2 to 40, n ₂ N is as follows ₄ Each independently represents an integer of 0 to 29, n ₂ +n ₄ The arrangement of the repeating units of- (A-O) -and- (B-O) -may be random or block, with an integer of 0 to 30. In the case of blocks, either of- (A-O) -and- (B-O) -may be on the bisphenyl side. n is n ₂ +n ₄ Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 0.n is n ₁ +n ₂ +n ₃ +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

The negative photosensitive layer may contain one kind or two or more kinds of polymerizable compounds B1 alone.

From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 in the negative photosensitive layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the negative photosensitive layer. The upper limit of the content of the polymerizable compound B1 is not limited. From the viewpoints of transferability and edge melting resistance, the content of the polymerizable compound B1 in the negative photosensitive layer is preferably 70 mass% or less, more preferably 60 mass% or less, relative to the total mass of the negative photosensitive layer.

In the negative photosensitive layer, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, and particularly preferably 60 mass% or more, from the viewpoint of more excellent resolution. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. From the viewpoint of releasability, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99 mass% or less, more preferably 95 mass% or less, still more preferably 90 mass% or less, and particularly preferably 85 mass% or less.

The negative photosensitive layer may contain a polymerizable compound B1 and a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (i.e., compounds having 1 ethylenically unsaturated group in one molecule), 2-functional ethylenically unsaturated compounds having no aromatic ring (i.e., compounds having 2 ethylenically unsaturated groups in one molecule), and 3-functional or more ethylenically unsaturated compounds (i.e., compounds having 3 or more ethylenically unsaturated groups in one molecule).

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, amine ester di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of alkylene glycol di (meth) acrylates include tricyclodecane dimethanol diacrylate (A-DCP, shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, shin-Nakamura Chemica ] Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shjn-Nakamura Chemical Co., ltd.), ethylene glycol dimethacrylate, 1, 10-decane diol diacrylate and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.

Examples of the amine ester di (meth) acrylate include propylene oxide modified amine ester di (meth) acrylate and ethylene oxide and propylene oxide modified amine ester di (meth) acrylate. Examples of commercial products include 8UX-015A (Taisei Fine Chemical Co., ltd.), UA-32P (Shin-Nakamura Chemical Co., ltd.), and UA-1100H (Shin-Nakamura Chemical Co., ltd.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, neopentyl tetraol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof. In the present invention, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept containing tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate. In the present invention, "(tri/tetra) (meth) acrylate" is a concept containing tri (meth) acrylate and tetra (meth) acrylate.

Examples of the alkylene oxide modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (for example, KAYARAD (registered trademark) 135 manufactured by Nippon Kayaku co., ltd.) and Shin-Nakamura Chemical co., ltd. Manufactured a-9300-1 CL), alkylene oxide-modified (meth) acrylate compounds (for example, nippon Kayaku co., ltd. Manufactured KAYARAD RP-1040, shin-Nakamura Chemical co., ltd. Manufactured ATM-35E, shin-Nakamura Chemical co., ltd. Manufactured a-9300 and DAICEL-ALLNEX ltd., manufactured EBECRYL (registered trademark) 135), ethoxylated glycerol triacrylates (for example, shin-Nakamura Chemical co., ltd. Manufactured a-GLY-9E), arofix (registered trademark) T0-2349 (for example, shin-Nakamura Chemical co., ltagagi co., lteid.) and lteim (registered trademark) and lteim-520 co., lteim, and lteim (registered trademark).

Examples of the polymerizable compound B other than the polymerizable compound B1 include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

In one embodiment, the negative photosensitive layer preferably contains polymerizable compounds B1 and 3-functional or more ethylenically unsaturated compounds, and more preferably contains polymerizable compounds B1 and two or more 3-functional or more ethylenically unsaturated compounds. In the above embodiment, the mass ratio of the polymerizable compound B1 to the ethylenically unsaturated compound having 3 or more functions ([ total mass of the polymerizable compounds B1 ]: total mass of the ethylenically unsaturated compounds having 3 or more functions ] is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and particularly preferably 1.5:1 to 3:1.

In one embodiment, the negative photosensitive layer preferably contains an ethylenically unsaturated compound having an acid group, more preferably contains an ethylenically unsaturated compound having an acid group, and a compound represented by the following formula (M) (hereinafter, sometimes referred to as "compound M") from the viewpoints of strength, adhesion, development residue inhibition, and rust resistance of the obtained cured film. The compound represented by the following formula (M) is one of ethylenically unsaturated compounds.

Formula (M): q (Q) ² -R ¹ -Q ¹

In the formula (M), Q ¹ Q and Q ² Each independently represents (meth) acryloyloxy, R ¹ Represents a divalent linking group having a chain structure.

In the formula (M), Q is from the viewpoint of synthesis easiness ¹ Q and Q ² Preferably the same groups. From the standpoint of reactivity, Q ¹ Q and Q ² Preference is given to acryloyloxy.

In the formula (M), R is from the viewpoint of bending resistance of the obtained cured film ¹ Preferably a hydrocarbon group, an alkylene oxide alkylene (-L) ¹ -O-L ¹ (-) or polyalkylene-oxy-alkylene (- (L) ¹ -O) _p -L ¹ Preferably a hydrocarbon group having 2 to 20 carbon atoms or a polyalkylene oxide alkylene group, more preferably an alkylene group having 4 to 20 carbon atoms, particularly preferably 6 to 18 carbon atomsA linear alkylene group. The hydrocarbon group may contain, for example, a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. The hydrocarbon group is preferably an alkylene group or a group in which 2 or more alkylene groups and 1 or more arylene groups are combined, more preferably an alkylene group, and particularly preferably a linear alkylene group, from the viewpoint of the bending resistance of the resulting cured film. L (L) ¹ Each independently represents an alkylene group, preferably ethylene, propylene or butylene, more preferably ethylene or 1, 2-propylene. p represents an integer of 2 or more, preferably an integer of 2 to 10.

In the formula (M), from the viewpoint of the moisture permeability and bending resistance of the obtained cured film, Q is connected ¹ And Q is equal to ² The number of atoms of the shortest connecting chain is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, particularly preferably 8 to 12. In the present invention, "connection Q ¹ And Q is equal to ² The atomic number "of the shortest connecting chain between is the number of connecting chain and Q ¹ R of the connection ¹ Atomic to Q ² R of the connection ¹ The shortest number of atoms up to the atom.

Examples of the compound M include 1, 3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyltetraol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 7-heptanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. From the viewpoint of the bending resistance of the resulting cured film, the compound M is preferably at least one selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentanediol di (meth) acrylate, more preferably at least one selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate, and particularly preferably at least one selected from the group consisting of 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate.

The negative photosensitive layer may contain one or two or more compounds M alone.

From the viewpoints of the moisture permeability and bending resistance of the obtained cured film, the content of the compound M is preferably 10 to 90 mass%, more preferably 15 to 70 mass%, even more preferably 20 to 50 mass%, and particularly preferably 25 to 35 mass% relative to the total mass of the ethylenically unsaturated compounds in the negative photosensitive layer.

From the viewpoints of the moisture permeability and bending resistance of the obtained cured film, the content of the compound M is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, even more preferably 5 to 20 mass%, and particularly preferably 6 to 14.5 mass% relative to the total mass of the negative photosensitive layer.

The molecular weight of the polymerizable compound B is preferably less than 5,000, more preferably 200 to 3,000, still more preferably 280 to 2,200, particularly preferably 300 to 2,200.

The negative photosensitive layer may contain one or two or more kinds of polymerizable compounds B alone.

The content of the polymerizable compound B in the negative photosensitive layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the negative photosensitive layer.

Photopolymerization initiator

The negative photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound (e.g., polymerizable compound B) by exposure to active light (e.g., ultraviolet rays, visible rays, and X-rays).

The kind of photopolymerization initiator is not limited. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photo-cationic polymerization initiator. From the viewpoint of hardenability, the photopolymerization initiator is preferably a photo radical polymerization initiator.

Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

From the viewpoints of photosensitivity, visibility of an exposed portion, visibility of a non-exposed portion, and resolution, the negative photosensitive layer preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives of 2,4, 5-triarylimidazole dimer as a photoradical polymerization initiator. In addition, 2,4, 5-triarylimidazole structures in the 2,4, 5-triarylimidazole dimer and the derivative thereof may be the same or different.

Examples of the derivative of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

Examples of the photo radical polymerization initiator include those described in paragraphs 0031 to 0042 of JP 2011-95716 and in paragraphs 0064 to 0081 of JP 2015-14783.

Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p' -dimethoxybenzyl) anisyl ester and benzophenone.

Examples of the commercially available photo radical polymerization initiator include TAZ-110 (Midoti Kagaku Co., ltd.), TAZ-111 (Midori Kagaku Co., ltd.), 1- [4- (phenylthio) ] phenyl-1, 2-octanedione-2- (0-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone- - (0-acetyl oxime) (trade name: IRGACURE OXE-02, BASF corporation), IRGACURE OXE-03 (BASF corporation), IRGACURE OXE-04 (BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-trade name (Omni rad 379EG,IGM Resins B.V), 2-methyl-1- (4-methylphenyl) -2-hydroxy-2- (Om-3-yl) ethanone- (0-acetyl oxime) (trade name: IRGACURE OX-02, BASF corporation), IRGACURE OXE-04 (BASF corporation), 2- (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-trade name (Omni-hydroxy-3-propanone (trade name: om-3, 3-hydroxy-2- (2-methylbenzoyl) hydroxy-1- (2-methyl) propanone), IGM Resins b.v. company), 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone-1 (trade name: 0mnirad 369,IGM Resins B.V company), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173,IGM Resins B.V, company), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad184, IGM Resins b.v. company), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651,IGM Resins B.V, company), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (trade name: omnirad TPO H, IGM Resins b.v. company), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819,IGM Resins B.V company), oxime ester-based photopolymerization initiator (trade name: lunar 6, dksh Japan k.k.), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole (individually: 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, trade name: B-CIM, hampford corporation) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd.).

The photoradical polymerization initiator preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives of 2,4, 5-triarylimidazole dimer.

The negative photosensitive layer preferably contains a photo-cationic polymerization initiator from the viewpoints of strength and durability as a permanent film of the obtained resin pattern.

As the photo-cationic polymerization initiator (i.e., photoacid generator), a compound that generates an acid in response to an active light having a wavelength of 300nm or more (preferably, an active light having a wavelength of 300nm to 450 nm) is preferable. The photo-cation polymerization initiator which does not directly react with the active light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by reacting with the sensitizer and reacting with the active light having a wavelength of 300nm or more.

Examples of the photo-cationic polymerization initiator include an aromatic iodonium complex salt and an aromatic sulfonium complex salt.

Examples of the aromatic iodonium salts include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (4-nonylphenyl) iodonium hexafluorophosphate, tolylisopropylphenyl iodonium tetrakis (pentafluorophenyl) borate (Rhodia, trade name: RHODORIL PI 2074) and tris (trifluoromethylsulfonyl) methanedi (4-tert-butyl) iodonium (di (4-tert-butyl) iodoniumtris (trifluoromethanesulfonyl) methanide) (BASF, trade name: CGI BBI-C1).

Examples of the aromatic sulfonium complex salt include 4-thio-phenyl diphenyl sulfonium hexafluoroantimonate (San-Apro ltd., trade name: CPI-101A), thio-phenyl diphenyl sulfonium tris (pentafluoroethyl) trifluorophosphate (San-Apro ltd., trade name: CPI-210S), 4- {4- (2-chlorobenzoyl) phenylthio } phenyl bis (4-fluorophenyl) sulfonium hexafluoroantimonate (ADEKA CORPORATION, trade name: SP-172), a mixture of aromatic sulfonium hexafluoroantimonates containing 4-thio-phenyl diphenyl sulfonium hexafluoroantimonate (ACETO Corporate USA, trade name: CPI-6976), tris (trifluoromethanesulfonyl) methanation triphenylsulfonium (BASF, trade name: CGI TPS-C1), tris [4- (4-acetylphenyl) sulfonium ] tris (trifluoromethanesulfonyl) methide (BASF, trade name: GSID 26-1) and tris [4- (4-acetylphenyl) sulfonium ] tetrakis (3, 5, 6-pentafluorophenyl) sulfonium penta (BASF, trade name: g, and 6, 5, 6-pentafluoro (BASF).

From the viewpoints of vertical rectangle processability and thermal stability, the photo cation polymerization initiator is preferably an aromatic sulfonium complex salt, more preferably 4- {4- (2-chlorobenzoyl) phenylthio } phenyl bis (4-fluorophenyl) sulfonium hexafluoroantimonate, a mixture of aromatic sulfonium hexafluoroantimonates containing 4-thiophenyl diphenyl sulfonium hexafluoroantimonate or tris [4- (4-acetylphenyl) sulfonylphenyl ] sulfonium tetrakis (2, 3,4,5, 6-pentafluorophenyl) borate.

The photo-cationic polymerization initiator is preferably a photo-cationic polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cationic polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cationic polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not limited. The pKa of the acid generated from the photo-cationic polymerization initiator is, for example, preferably-10.0 or more.

Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator.

Examples of the ionic photo-cationic polymerization initiator include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonium salt compounds) and quaternary ammonium salt compounds. Examples of the ionic photo-cationic polymerization initiator include those described in paragraphs 0114 to 0133 of JP-A2014-85643.

Examples of the nonionic cationic polymerization initiator include trichloromethyl-s-triazine compound, diazomethane compound, imide sulfonate compound and oxime sulfonate compound. Examples of the trichloromethyl-s-triazine compound, the diazomethane compound and the imide sulfonate compound include those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494. Examples of the oxime sulfonate compound include those described in paragraphs 0084 to 0088 of International publication No. 2018/179640.

The negative photosensitive layer may contain one kind or two or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator in the negative photosensitive layer is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and particularly preferably 1.0 mass% or more, based on the total mass of the negative photosensitive layer. The upper limit of the content of the photopolymerization initiator is not limited. The content of the photopolymerization initiator is preferably 10 mass% or less, more preferably 5 mass% or less, based on the total mass of the negative photosensitive layer.

Multifunctional epoxy resins

The negative photosensitive layer preferably contains a multifunctional epoxy resin from the viewpoints of strength and durability as a permanent film of the obtained resin pattern. The multifunctional epoxy resin is a compound having 2 or more epoxy groups in one molecule.

From the viewpoint of obtaining a sufficient curing speed, the epoxy equivalent of the multifunctional epoxy resin is preferably 100 g/equivalent to 500 g/equivalent, more preferably 100 g/equivalent to 300 g/equivalent. The epoxy equivalent is a value measured by a method in accordance with "JIS K-7236".

From the viewpoint of developability, the multifunctional epoxy resin is preferably in a liquid state at ordinary temperature (i.e., 25 ℃). The viscosity of the multifunctional epoxy resin at 25℃is preferably 5,000 mPas or less, more preferably 1,000 mPas or less.

Examples of the type of the multifunctional epoxy resin include a glycidyl ether type, a glycidyl ester type, a glycidyl amine type and an alicyclic type. The propylene oxide type or the propylene oxide ester type is preferable, and the propylene oxide ether type is more preferable from the viewpoint of good liquid storage stability.

Examples of the epoxypropyl ether type polyfunctional epoxy resin include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, neopentylglycol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

Examples of the epoxypropyl ester type polyfunctional epoxy resin include diglycidyl phthalate, diglycidyl tetrahydrophthalate, and diglycidyl hexahydrophthalate.

Examples of the polyfunctional epoxy resin include an epoxy compound having at least 2 oxirane groups in one molecule and an epoxy compound having at least 2 epoxy groups having an alkyl group in β -position in one molecule.

Examples of the epoxy compound having at least 2 ethylene oxide groups in one molecule include bisphenol F type epoxy resin (for example, NIPPON STEEL Chemical & Material co., YDF-170 manufactured by ltd.), bixylenol type or biphenol type epoxy resin (for example, YX4000 manufactured by Mitsubishi Chemical Corporation) or a mixture thereof, heterocyclic type epoxy resin having an isocyanurate skeleton (for example, ARALDITE PT810 manufactured by TEPIC and Huntsman Advanced Materials manufactured by Nissan Chemical Corporation), bisphenol a type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, highly halogenated epoxy resin and brominated phenol novolac type epoxy resin), allyl group-containing bisphenol a type epoxy resin, triphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenolbiphenylene type epoxy resin, dicyclopentadiene type epoxy resin (e.g., HP-7200 and HP-7200H manufactured by DIC Corporation), glycidylamine type epoxy resin (e.g., diaminodiphenylmethane type epoxy resin, diglycidyl aniline and triglycidyl aminophenol), epoxypropyl ester type epoxy resin (e.g., diglycidyl phthalate, diglycidyl adipate, diglycidyl hexahydrophthalate and diglycidyl dimer acid), allantoin type epoxy resin, hydantoin type epoxy resin (e.g., 3, 4-epoxycyclohexylmethyl-3', 4' -epoxycyclohexane carboxylate, GT-300, GT-400 and ZEHPE3150 manufactured by bis (3, 4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide and Daicel Corporation), imide-type alicyclic epoxy resins, triphenylmethane type epoxy resins, bisphenol A novolac type epoxy resins, tetraphenolethane (tetraphenylol ethane) type epoxy resins, epoxypropyl phthalate resins, epoxypropyl tetraepoxyxylenol ethane resins, naphthalene group-containing epoxy resins (e.g., naphthol aralkyl type epoxy resins, naphthol novolac type epoxy resins, 4-functional naphthalene type epoxy resins, NIPPON STEEL Chemical & Material Co., ESN-190 and ESN-360 manufactured by Ltd. And HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation), epoxy resins and diene compounds (e.g., reactant of a polyphenol compound obtained by addition reaction of divinylbenzene and dicyclopentadiene) with epichlorohydrin, compound obtained by epoxidizing a ring-opened polymer of 4-vinylcyclohexene-1-oxide using peracetic acid, 8-functional bisphenol a novolac type epoxy resin (for example, EPON SU-8 manufactured by Resolution Performamce Products, LLC), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, nippon Kayaku co., ltd. Manufactured NER-7604), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol a type epoxy resin with epichlorohydrin (for example, nippon Kayaku co., ltd. Manufactured NER-1302), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol a type epoxy resin with epichlorohydrin (for example, nippon Kayaku co., ltd. Manufactured by netd. Manufactured by netr-1302), O-cresol novolak type epoxy resins (for example, eopton Kayaku co., ltd. EOCN 4400), biphenol novolak type epoxy resins (for example, nippon Kayaku co., ltd. NC-3000H), epoxy resins having a cyclic phosphorus-containing structure, α -methyl stilbene type liquid crystal epoxy resins, dibenzoyloxy benzene type liquid crystal epoxy resins, azobenzene type liquid crystal epoxy resins, azophenyl type liquid crystal epoxy resins, binaphthyl type liquid crystal epoxy resins, azine type epoxy resins, glycidyl methacrylate type epoxy resins (for example, CP-50S and CP-50M manufactured by NOF CORPORATION), CP-50M, cyclohexylmaleimide type and glycidyl methacrylate type copolymerized epoxy resins, bis (glycidoxyphenyl) fluorene type epoxy resins and bis (glycidoxyphenyl) adamantane type epoxy resins, which are obtained by reacting a phenolic hydroxyl group of a resin obtained by reacting bis (methoxymethylphenyl) with phenol.

Among the epoxy compounds having at least 2 epoxy groups having an alkyl group at the β -position in one molecule, examples of the epoxy group having an alkyl group at the β -position include β -alkyl substituted epoxypropyl groups. The epoxy group may be at least 1 beta-alkyl-substituted epoxypropyl group. The epoxy groups may be all beta-alkyl-substituted epoxypropyl groups.

The negative photosensitive layer contains one or more polyfunctional epoxy resins alone.

The content of the multifunctional epoxy resin is preferably 10 to 90 mass%, more preferably 20 to 70 mass%, relative to the total mass of the negative photosensitive layer.

Hydroxyl-containing compounds

The negative photosensitive layer preferably contains a hydroxyl group-containing compound from the viewpoints of strength and durability as a permanent film of the obtained resin pattern. Examples of the hydroxyl group-containing compound include a polyol compound and a phenol compound.

The polyol compound contains a hydroxyl group that reacts with an epoxy group in the epoxy resin under the influence of an acid catalyst, and functions as a reactive diluent. The negative photosensitive layer preferably contains polycaprolactone polyol as the polyol compound. The negative photosensitive layer contains polycaprolactone polyol, and a dried coating film of the composition for forming the negative photosensitive layer is softened. As a result, cracking of the resin pattern as a permanent film can be prevented.

As the polyol compound, for example, a commercially available polyester polyol can be used. Examples of the commercially available polyester polyols include "PLACCEL205" having a molecular weight of 530 and an OH number (also referred to as "hydroxyl number") of 210mgKOH/g, "PLACCEL210" having a molecular weight of 1,000 and an OH number of 110mgKOH/g, and "PLACCEL220" having a molecular weight of 2,000 and an OH number of 56mgKOH/g (both manufactured by Daicel Corporation). Examples of the commercially available polyester polyols include "Capa2054" having a molecular weight of 550 and an OH number of 204mgKOH/g, "Capa2100" having a molecular weight of 1,000 and an OH number of 112mgKOH/g, and "Capa2200" having a molecular weight of 2,000 and an OH number of 56mgKOH/g (all manufactured by Perston corporation).

Examples of the phenol compound include phenol novolac resins, cresol novolac resins, polyfunctional bisphenol a novolac resins, biphenyl phenol novolac resins, phenol resins having a trihydroxy phenyl methane skeleton, and phenol resins having a terpene diphenol skeleton. Examples of the phenol compound include phenol resins obtained from phenols such as bisphenol a and bisphenol F.

The OH value of the hydroxyl group-containing compound is preferably from 90mgKOH/g to 300mgKOH/g, more preferably from 100mgKOH/g to 250mgKOH/g.

The negative photosensitive layer may contain a single kind or two or more kinds of hydroxyl group-containing compounds.

The content of the hydroxyl group-containing compound is preferably 1 to 35 mass%, more preferably 5 to 25 mass%, based on the total mass of the negative photosensitive layer.

Metal oxidation inhibitor

The negative photosensitive layer preferably contains a metal oxidation inhibitor. The metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule. The aromatic ring containing a nitrogen atom is preferably at least one selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and condensed rings of these rings with other aromatic rings, and more preferably an imidazole ring or a condensed ring of an imidazole ring with other aromatic rings. The other aromatic ring may be an aromatic ring containing one element in the ring or an aromatic ring containing two or more elements in the ring (i.e., a heterocyclic ring). The other aromatic ring is preferably an aromatic ring containing one element in the ring, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

Examples of the preferable metal oxidation inhibitor include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole. The metal oxidation inhibitor is preferably at least one selected from imidazole, benzimidazole and benzotriazole. As a commercially available benzotriazole, for example, BT-120 manufactured by Johoku Chemical Co., ltd.

The metal oxidation inhibitor is preferably at least one selected from the group consisting of benzotriazole compounds and carboxybenzotriazole compounds.

Examples of the benzotriazole compounds include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

Examples of the carboxybenzotriazole compound include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. Examples of the commercial product of the carboxybenzotriazole compound include CBT-1 (Johoku Chemical Co., ltd.).

The negative photosensitive layer may contain one kind or two or more kinds of metal oxidation inhibitors.

The content of the metal oxidation inhibitor is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and particularly preferably 1 to 5 mass%, relative to the total mass of the negative photosensitive layer.

Other ingredients-

The negative photosensitive layer may contain other components than the above components. Examples of the other component include a dye, a surfactant, a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a resin, and a solvent.

From the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution, the negative photosensitive layer preferably contains a dye (hereinafter, sometimes simply referred to as "dye NC") having a maximum absorption wavelength of 450nm or more and a maximum absorption wavelength that changes due to an acid, a base, or a radical in a wavelength range of 400nm to 780nm at the time of development. Although the detailed mechanism is not clear, the negative photosensitive layer contains the dye NC, so that the adhesion between the negative photosensitive layer and the layer adjacent to the negative photosensitive layer is improved, and the resolution is more excellent.

In the present invention, the term "the maximum absorption wavelength varies depending on the acid, the base or the radical" used in relation to the pigment may refer to any of modes 1, 2 and 3. The 1 st aspect is an aspect in which the coloring matter in a developed state is decolorized by an acid, a base or a radical. The 2 nd aspect is an aspect in which the color of the dye in a decolored state is developed by an acid, a base or a radical. The 3 rd aspect is an aspect in which the coloring matter in the color development state changes to a color development state of another hue.

The dye NC may be a compound which develops color by exposure to light from a decolored state or a compound which is decolored by exposure to light from a decolored state. The dye NC may be a dye which changes in color or decolored state by an acid, a base or a radical generated by exposure. The dye NC may be a dye whose state (for example, pH) changes in the negative photosensitive layer under an acid, alkali or radical generated by exposure, and thus the state of color development or decoloration changes. The dye NC may be a dye which changes its state by directly being stimulated by an acid, an alkali or a radical to develop or decolor without exposure.

From the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the dye NC is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.

From the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution, the dye NC is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye whose color is developed by a radical.

From the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the dye NC preferably contains both a dye whose maximum absorption wavelength is changed by radicals and a photo radical polymerization initiator.

From the viewpoints of visibility of the exposed portion and visibility of the non-exposed portion, the dye NC is preferably a dye that develops color by an acid, a base, or a radical.

Free radicals, acids or bases are generated from the photo-radical polymerization initiator, the photo-cationic polymerization initiator or the photo-base generator by exposing the negative photosensitive layer containing the photo-radical polymerization initiator, the photo-cationic polymerization initiator (i.e., photo-acid generator) or the photo-base generator. Examples of the color development pattern of the dye NC include a pattern in which a radical, an acid or a base is generated from a radical reactive dye, an acid reactive dye or a base reactive dye (for example, a leuco dye).

In the dye NC, from the viewpoint of visibility of an exposed portion and visibility of a non-exposed portion, a maximum absorption wavelength in a wavelength range of 400nm to 780nm at the time of color development is preferably 550nm or more, more preferably 550nm to 700nm, and particularly preferably 550 to 650nm.

In the dye NC, the number of maximum absorption wavelengths in the wavelength range of 400nm to 780nm at the time of color development may be 1 or 2 or more. When the dye NC has a maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development of 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the dye NC is measured by measuring the transmission spectrum of a solution containing the dye NC (liquid temperature: 25 ℃) in the range of 400nm to 780nm using a spectrophotometer (for example, UV3100, shimadzu Corporation) under an atmospheric atmosphere, and then detecting the wavelength at which the intensity of light becomes extremely small (i.e., the maximum absorption wavelength).

Examples of the coloring matter which develops or discolors by exposure to light include colorless compounds. Examples of the coloring matter which is decolorized by exposure to light include colorless compounds, diarylmethane-based coloring matters, oxazine-based coloring matters, xanthene-based coloring matters, iminonaphthoquinone-based coloring matters, azomethine-based coloring matters, and anthraquinone-based coloring matters. The dye NC is preferably a colorless compound from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (i.e., triarylmethane-based dye), a colorless compound having a spiropyran skeleton (i.e., spiropyran-based dye), a colorless compound having a fluoran skeleton (i.e., fluoran-based dye), a colorless compound having a diarylmethane skeleton (i.e., diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (i.e., rhodamine lactam-based dye), a colorless compound having an indolylphthalate (phtha) skeleton (i.e., indolylphthalate-based dye), and a colorless compound having a leuco golden amine (leuko auramine) skeleton (i.e., leucogolden amine-based dye). The colorless compound is preferably a triarylmethane dye or a fluoran dye, and more preferably a colorless compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluoran dye.

The colorless compound preferably has a lactone ring, a sultone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and visibility of a non-exposed portion. The lactone ring, sulfenalactone ring or sultone ring contained in the colorless compound reacts with a radical generated from a photo radical polymerization initiator or an acid generated from a photo cation polymerization initiator. This makes it possible to decolorize the colorless compound by changing the colorless compound to a closed-loop state, or to develop the colorless compound by changing the colorless compound to an open-loop state. The colorless compound is preferably the 1 st compound, more preferably the 2 nd compound. The 1 st compound has a lactone ring, a sulfenamide ring or a sultone ring, and the lactone ring, the sulfenamide ring or the sultone ring develops color due to free radical or acid ring opening. The compound 2 has a lactone ring, and the lactone ring develops color due to free radical or acid ring opening.

Examples of the colorless compound include p, p', p "-hexamethyltriphenylamine methane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy corporation), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidinyl) fluoran, 3, 6-dimethoxy fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-amino fluoran, 3- (N, N-diethylamino) -6-methyl-7-chloro fluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylamino fluoran, 3- (N, N-diethylamino) -6-methyl-7-chloro fluoran, 3- (N, N-diethylamino) -6-methyl-7-fluoran, n-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-stubble aminofluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalate, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalate, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalate, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azo phthalate, 3- (4-ethyl-2-methylindol-3-yl) phthalate, 3- (1-ethyl-2-methylindol-3-yl) phthalate, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

Examples of the dye NC include dyes. Examples of dyes include bright green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), mitsunin yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol blue, methyl orange, para-methyl red, congo red, benzorhodopsin (benzopurline) 4B, alpha-naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), accessory red (paramfuchsin), victorian pure blue (victoria pure blue) -naphthalene sulfonate, victorian pure blue BOH (Hodogaya Chemical co., ltd.), oil blue #603 (Orient Chemical Industries co., ltd), pink red 312 (Orient Chemical Industries co.), oil red # 5B, benzopurplish red (26-35B), oil red (ltd), 6-carboxyls) 2B, p-carboxyls (24-4G, p-carboxyls) 2, p-carboxyls (54-4G, p-carboxyls) 2, p-carboxyls (6-carboxyls) 2, p-carboxyls) 4G, p-carboxyls (6, 4-carboxyls) 2, 4-carboxyls (p-carboxyls) and (p-carboxyls) 2, 4-carboxyls) of these dyes, n-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-beta-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

The dye NC is preferably at least one selected from the group consisting of leuco crystal violet, crystal violet lactone, brilliant green and victoria pure blue-naphthalene sulfonate.

The negative photosensitive layer may contain one or two or more pigments.

From the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution, the content of the dye is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, still more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the negative photosensitive layer.

The content of the dye NC means the content of the dye when all the dye NC contained in the negative photosensitive layer is in a color development state. Hereinafter, a method for determining the content of the dye NC will be described by taking a dye that develops color due to radicals as an example. Solutions were prepared in which pigment (0.001 g) was dissolved in methyl ethyl ketone (100 mL) and pigment (0.01 g) was dissolved in methyl ethyl ketone (100 mL). After IRGACURE OXE-01 (BASF corporation) was added as a photo radical polymerization initiator to each of the obtained solutions, light of 365nm was irradiated to generate radicals, and all the pigments were brought into a colored state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under an air atmosphere using a spectrophotometer (for example, UV3100, shimadzu Corporation), and a calibration curve was prepared. Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above, except that the negative photosensitive layer (3 g) was dissolved in methyl ethyl ketone instead of the pigments. From the absorbance of the obtained solution containing the negative photosensitive layer, the content of the pigment contained in the negative photosensitive layer was calculated from the calibration curve.

From the viewpoint of uniformity of thickness, the negative photosensitive layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkyl phenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone nonionic surfactants, and fluorine nonionic surfactants.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate and glycerin ethoxylate).

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.

Examples of the commercial products of the nonionic surfactants include PLURONIC (for example, L10, L31, L61, L62, 10R5, 17R2 and 25R2, BASF), TETRONIC (for example, 304, 701, 704, 901, 904 and 150R1, BASF), solsperse 20000 (The Lubrizol Corporation), NCW-101 (FUJIFILM Wako Pure Chemical Corporation), NCW-1001 (FUJIFILM Wako Pure Chemical Corporation), NCW-1002 (FUJIFILM Wako Pure Chemical Corporation), PIONIN (for example, D-6112-W and D-6315,Takemoto Oil&Fat Co, ltd.), OLFIN E1010 (Nissin Chemical Co., ltd.) and Surfynol (for example, 104, 400 and 440,Nissin Chemical Co, ltd.).

The surfactant is preferably at least one selected from fluorine-based surfactants and silicone-based surfactants.

Examples of the commercial products of the fluorine-based surfactants include MEGAFACE (for example, F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21,DIC Corporation), fluorad (for example, FC430, FC431 and FC171,3M Japan Limited), surflon (e.g., S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40, AGC Inc.), polyFox (e.g., PF636, PF656, PF6320, PF6520 and PF7002, OMNOVA So ] processes Inc.) and Ftergent (710 FM, 610FM, 601AD, ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC and 681,NEOS COMPANY LIMITED).

The fluorine-based surfactant is preferably an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, and the functional group containing a fluorine atom is partially cleaved when heat is applied, whereby the fluorine atom volatilizes. Examples of the fluorine-based surfactant include MEGAFACE DS series (chemical industry daily report (2016, 2, 22 days) and daily industrial news (2016, 2, 23 days) manufactured by DIC Corporation, for example MEGAFACE DS-21).

The fluorine-based surfactant is also preferably a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound, each of which has a fluorinated alkyl group or a fluorinated alkylene ether group.

The fluorine-based surfactant may be a block polymer. The fluorine-based surfactant is preferably a fluorine-containing polymer compound, and more preferably the fluorine-containing polymer compound contains a 1 st structural unit derived from a (meth) acrylate compound having a fluorine atom and a 2 nd structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).

The fluorine-based surfactant may be a fluoropolymer having a group containing an ethylenic unsaturated bond in a side chain. Examples of the fluorine-based surfactant include MEGAFACE (for example, RS-101, RS-102, RS-718K and RS-72-K, DIC Corporation).

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having an organic group introduced into a side chain or a terminal.

Examples of the commercially available silicone surfactants include DOWSIL 8032ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH28PA, toray Silicone SH29PA, toray Silicone SH30PA, and Toray Silicone SH8400 (DuPont Toray Specialty Materials K.K. above). Examples of the commercially available silicone surfactants include X-22-4952, X-22-4272, X-22-6266, KF-351A, K, L, KF-355, A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (Shin-Etsu Chemical Co., ltd.). Examples of the commercially available silicone surfactants include F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (Momentive Performance Materials Inc. above). Examples of the silicone surfactant include BYK307, BYK323, and BYK330 (BYK Chemie corporation).

From the viewpoint of more excellent resolution, the negative photosensitive layer preferably contains a fluorine-based nonionic surfactant. It is considered that the negative photosensitive layer contains a fluorine-based nonionic surfactant, so that the etching solution is prevented from penetrating into the negative photosensitive layer and thus undercut is reduced. Examples of the commercial products of the fluorine-based nonionic surfactant include MEGAFACE (registered trademark) F-551 (DIC Corporation), MEGAFACE F-552 (DIC Corporation) and MEGAFACE F-554 (DIC Corporation).

Examples of the surfactant include surfactants described in paragraphs 0060 to 0071 of JP-A-4502784, paragraph 0017 and JP-A-2009-237362.

From the viewpoint of improving the environmental suitability, the fluorine-based surfactant is preferably a surfactant derived from a substitute material for a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

The negative photosensitive layer may contain one or two or more surfactants alone.

When the negative photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass%, more preferably 0.05 to 1.0 mass%, and particularly preferably 0.10 to 0.80 mass% based on the total mass of the negative photosensitive layer.

The negative photosensitive layer may contain a radical inhibitor. Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenazine or 4-methoxyphenol. Examples of the radical polymerization inhibitor include naphthylamine, copper (I) chloride, aluminum nitrosophenyl hydroxylamine salt and diphenylnitrosoamine. In order not to impair the sensitivity of the negative photosensitive layer, nitrosophenyl hydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.

The ratio of the total content of the radical inhibitor, the benzotriazole compound and the carboxybenzotriazole compound to the total mass of the negative photosensitive layer is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%. From the viewpoint of imparting storage stability to the negative photosensitive layer, the ratio of the total content of the above components is preferably 0.01 mass% or more. On the other hand, from the viewpoint of suppressing discoloration of the dye while maintaining sensitivity, the ratio of the total content of the above components is preferably 3 mass% or less.

The negative photosensitive layer may contain a sensitizer. As the sensitizer, for example, a known sensitizer can be used. Dyes and pigments may also be used as sensitizers. Examples of the sensitizer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone (xanthone) compound, a thioxanthone (thioxanthone) compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (for example, 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.

The negative photosensitive layer may contain one or more sensitizer.

When the negative photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing speed by balancing the polymerization speed and chain transfer, the content is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the negative photosensitive layer.

The negative photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and the heterocyclic compound include those described in paragraphs 0097 to 0103 and 0111 to 0118 of International publication No. 2018/179640.

The negative photosensitive layer may contain a resin. Examples of the resin include acrylic resins, styrene-acrylic copolymers (but are limited to copolymers having a styrene content of 40 mass% or less), polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The negative photosensitive layer may contain a solvent. When the negative photosensitive layer is formed using a composition containing a solvent, the solvent may remain in the negative photosensitive layer. As the solvent, the following will be described.

The water content in the negative photosensitive layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, from the viewpoint of improving reliability and lamination.

The negative photosensitive layer may contain, for example, at least one additive selected from the group consisting of metal oxide particles, antioxidants, dispersants, acid breeder agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, organic anti-settling agents, and inorganic anti-settling agents. The additives are described in, for example, paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643. The contents of the above publications are incorporated by reference into the present specification.

The negative photosensitive layer may contain a predetermined amount of impurities. Examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among the above impurities, the halide ion, sodium ion and potassium ion are easily mixed in the form of impurities, and therefore, the following contents are preferable.

The content of impurities in the negative photosensitive layer is preferably 80ppm or less, more preferably 10ppm or less, and still more preferably 2ppm or less, on a mass basis. The content of impurities in the negative photosensitive layer may be 1ppb or more or 0.1ppm or more on a mass basis.

As a method for adjusting the impurity in the above range, a raw material having a small impurity content is selected as a raw material for the negative photosensitive layer, and the manufacturing equipment is cleaned to remove the impurity while preventing the impurity from being mixed in when the negative photosensitive layer is formed. By this method, the impurity amount can be adjusted within the above-described range.

The impurities can be quantified by a known method such as ICP (Inductively Coupled P asa: inductively coupled plasma) luminescence spectrometry, atomic absorption spectrometry or ion chromatography.

The negative photosensitive layer preferably contains a small amount of benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chlorine, N-dimethylformamide, N-dimethylacetamide and hexane. The content of the compound in the negative photosensitive layer is preferably 100ppm or less, more preferably 20ppm or less, and particularly preferably 4ppm or less on a mass basis. The content of the compound in the negative photosensitive layer may be 10ppb or more or 100ppb or more on a mass basis. The content of the above-mentioned compound can be determined by a known measurement method. The content of the compound can be suppressed by the same method as the method for adjusting the content of the impurity of the metal.

Thickness of negative photosensitive layer

The thickness of the negative photosensitive layer is not limited. The thickness of the negative photosensitive layer may be determined, for example, in the range of 1 μm to 100 μm.

Method for forming negative photosensitive layer

The negative photosensitive layer can be formed, for example, by preparing a composition containing a component for forming the negative photosensitive layer and a solvent, then applying the composition to an object to be coated (for example, a substrate), and drying the composition. In the preparation of the composition, for example, the composition may be prepared by dissolving each component in a solvent, and mixing the obtained solutions in a predetermined ratio. The composition may be filtered, for example, using a filter having a pore size of 0.2 μm to 30 μm.

The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the component forming the negative photosensitive layer. Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

The composition preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, the composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent. The composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.

As the solvent, the solvents described in paragraphs 0092 to 0094 of International publication No. 2018/179640 and the solvents described in paragraph 0014 of Japanese patent application laid-open No. 2018-177889 may be used. The contents of their publications are incorporated by reference into the present specification.

The composition may contain a single solvent or two or more solvents.

The negative photosensitive layer in contact with the photomask may be a negative photosensitive layer transferred onto a transfer target (e.g., a substrate) using a photosensitive transfer material (hereinafter referred to as "transfer material" in this paragraph). As the transfer material, a known transfer material can be used. Examples of the transfer material include a temporary support and a negative photosensitive layer. For example, a transfer material including a temporary support and a negative photosensitive layer can be produced by preparing a composition containing a component for forming a negative photosensitive layer and a solvent, applying the composition to the temporary support, and drying the composition. Next, a method of using the transfer material will be described. For example, in a method of transferring a negative photosensitive layer to a transfer target using a transfer material including a temporary support and a negative photosensitive layer, the negative photosensitive layer of the transfer material is brought into contact with the transfer target by bonding the transfer material to the transfer target, and then the temporary support is peeled off from the negative photosensitive layer, whereby the negative photosensitive layer can be disposed on the transfer target. As a method of bonding the transfer material to the transfer target, a known method can be used. The transfer material is preferably bonded to the transfer target under pressure and heat. The transfer material and the transfer target can be bonded using, for example, a laminator, a vacuum laminator, or an automatic cutting laminator that can further improve productivity.

(general hardness)

The general hardness of the photosensitive layer measured according to the test load when the press-in depth is 1/10 of the thickness of the photosensitive layer in the press-in test is preferably 5.0N/mm ² The above is more preferably 7.0N/mm ² The above is particularly preferably 9.0N/mm ² The above. The general hardness through the photosensitive layer was 5.0N/mm ² As described above, the smoothness of the photomask to the photosensitive layer is improved, and deformation of the photosensitive layer during contact exposure is suppressed. In other words, in the contact exposure, the following property of the photosensitive layer to the surface shape of the photomask is reduced. As a result, the adhesiveness of the photosensitive layer to the photomask is further reduced. The upper limit of the general hardness of the photosensitive layer is not limited. From the viewpoint of winding in the roll-to-roll process, the general hardness of the photosensitive layer is preferably 100.0N/mm ² Hereinafter, it is more preferably 50.0N/mm ² Hereinafter, it is particularly preferably 20.0N/mm ² The following is given.

In the present invention, the general hardness of the photosensitive layer is measured by the following method. A photosensitive layer to be measured for general hardness is formed on a PET film (for example, cosmosfine a4300 (Toyobo co., ltd.)). Examples of the method for forming the photosensitive layer include a method of applying a composition containing a component for forming the photosensitive layer using a bar coater and drying the composition, and a method of transferring a photosensitive transfer material using a laminator. A spherical indenter (diameter: 0.4 mm) was attached to an HM2000 type durometer manufactured by FISCHER INSTRUMENTS K.K., and the indentation test was performed at 23℃and 50% RH (relative humidity). The press-in test was performed until the maximum load was reached while the load was increased stepwise. In the press-in test, the loading time was set to 10 seconds, and the creep time was set to 5 seconds. According to the spherical pressure head contacted with the photosensitive layer The test load when the surface area and the press-in depth of the photosensitive layer before the test were 1/10 of the thickness of the photosensitive layer was measured to determine the general hardness (unit: N/mm ² ). The 10-time press-in test was repeated to obtain an arithmetic average of general hardness of the photosensitive layer.

Modification of the invention

In the exposure method according to an embodiment of the present invention, a laminate including a photosensitive layer and another layer may be used. When a laminate including a photosensitive layer and another layer is used, the photomask may be in contact with the photosensitive layer via the other layer. That is, the photomask may be in contact with other layers. When a laminate including a photosensitive layer and another layer is used, the photosensitive layer may be exposed to light through a photomask and the other layer. Examples of the other layer include a temporary support and a resin layer. However, the types of other layers are not limited to the above layers. As the other layer, for example, a layer disposed between a photomask and a photosensitive layer in a known exposure method of the photosensitive layer can be used. Hereinafter, an exposure method using a laminate including a photosensitive layer and other layers will be described. The embodiment of the exposure method (for example, the contact method and the exposure conditions) using the laminate including the photosensitive layer and the other layers follows the above-described matters except for the matters described below.

The exposure method according to an embodiment of the present invention preferably includes: a 6 th preparation step, a 7 th preparation step, and a 2 nd exposure step. In the 6 th preparation step, a photomask according to an embodiment of the present invention is prepared. In the 7 th preparation step, a laminate including a photosensitive layer and a temporary support in this order is prepared. In the 2 nd exposure step, the photomask is brought into contact with the temporary support, and the photosensitive layer is exposed through the photomask and the temporary support. The method of exposing the photosensitive layer through the temporary support can suppress contamination of the photomask.

The exposure method according to an embodiment of the present invention preferably includes: an 8 th preparation step, a 9 th preparation step, a 1 st exposure step, and a 3 rd exposure step. In the 8 th preparation step, a photomask according to an embodiment of the present invention is prepared. In the 9 th preparation step, a laminate including a photosensitive layer and a temporary support in this order is prepared. In the 1 st exposure step, the temporary support is peeled off to expose the surface of the photosensitive layer. In the 3 rd exposure step, the photomask is brought into contact with the surface of the photosensitive layer exposed by the peeling of the temporary support, and the photosensitive layer is exposed through the photomask.

The laminate used in the exposure method may further include a resin layer between the photosensitive layer and the temporary support. When a laminate including a resin layer between a photosensitive layer and a temporary support is used, the photosensitive layer is exposed to light through a photomask and the resin layer in the 1 st exposure step. For example, when the photosensitive layer is exposed without peeling off the temporary support, the photosensitive layer is exposed through the photomask, the temporary support, and the resin layer. For example, when the photosensitive layer is exposed after the temporary support is peeled off, the photomask is brought into contact with the resin layer (specifically, the surface of the resin layer exposed by the peeling off of the temporary support), and the photosensitive layer is exposed through the photomask and the resin layer. The laminate used in the exposure method may include a substrate, a photosensitive layer, and a temporary support in this order.

(temporary support)

The temporary support is a support that supports at least the photosensitive layer and can be peeled off.

The transmittance of the temporary support to the dominant wavelength of light used for exposure is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The transmittance of the temporary support was measured using MCPD Series manufactured by 0tsuka Electronics Co, ltd.

Examples of the temporary support include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and the like, a resin film is preferable. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film and polycarbonate film. The resin film is preferably a polyethylene terephthalate film, and more preferably a biaxially stretched polyethylene terephthalate film.

The thickness of the temporary support is not limited. The thickness of the temporary support may be determined, for example, by the strength, flexibility, and light transmittance. The thickness of the temporary support is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm from the viewpoints of ease of handling and versatility. The thickness of the temporary support is determined by arithmetically averaging the thickness of the temporary support measured at 10.

A preferable embodiment of the temporary support is described in paragraphs 0017 to 0018 of japanese patent application laid-open publication No. 2014-85643, for example. The content of this publication is incorporated by reference into the present specification.

(resin layer)

Examples of the resin contained in the resin layer include polyvinyl alcohol, polyvinylpyrrolidone, cellulose, polyacrylamide, polyethylene oxide, gelatin, polyvinyl ether, and polyamide. The resin layer preferably contains polyvinyl alcohol. The polyvinyl alcohol reduces the oxygen permeability of the resin layer. As a result, hardening inhibition of negative photosensitivity due to oxygen, for example, can be avoided. The resin contained in the resin layer is preferably a water-soluble resin. "Water-soluble" means that the solubility of 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more. The resin layer may contain one or two or more resins.

From the viewpoint of oxygen barrier properties, the content of the resin in the resin layer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total mass of the resin layer.

The resin layer preferably contains a surfactant. Examples of the surfactant include surfactants containing fluorine atoms and surfactants containing silicon atoms. The surfactant is preferably a surfactant containing a fluorine atom, more preferably a surfactant containing a perfluoroalkyl group and a polyalkylene oxide group. The surfactant may also be an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant. The surfactant is preferably a nonionic surfactant.

The universal hardness of the resin layer measured according to the test load at a press-in depth of 1/10 of the thickness of the resin layer in the press-in test is preferably 5.0N/mm ² The above is more preferably 7.0N/mm ² The above is particularly preferably 10.0N/mm ² The above. The general hardness through the resin layer was 5.0N/mm ² As described above, the smoothness of the photomask to the resin layer is improved, and deformation of the resin layer during contact exposure is suppressed. In other words, in the contact exposure, the following property of the resin layer to the surface shape of the photomask is reduced. As a result, the adhesiveness of the resin layer to the photomask is further reduced. The upper limit of the general hardness of the resin layer is not limited. From the viewpoint of winding in the roll-to-roll process, the general hardness of the resin layer is preferably 100.0N/mm ² Hereinafter, it is more preferably 50.0N/mm ² Hereinafter, it is particularly preferably 20.0N/mm ² The following is given. The universal hardness of the resin layer was measured by a method conforming to the method for measuring universal hardness of the photosensitive layer. Examples of the method for forming the layer include a method in which only the resin layer is peeled off and placed on the PET film to be easily adhered, and a method in which only the photosensitive layer of the transfer material is removed with a solvent.

The thickness of the resin layer is not limited. The thickness of the resin layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2 μm from the viewpoints of oxygen barrier property and resolution. The thickness of the resin layer can be measured by arithmetically averaging the thickness of the temporary support measured at 10.

Examples of the method for forming the resin layer include a method using a composition containing a component for forming the resin layer. For example, the resin layer is formed by coating and drying the composition. Examples of the composition include a composition containing a resin and any additives. In order to adjust the viscosity of the composition and to facilitate formation of the resin layer, the composition preferably contains a solvent. The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the resin. The solvent is preferably at least one selected from water and water-miscible organic solvents, and more preferably a mixed solvent containing water or a water-miscible organic solvent. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

(substrate)

The kind of the substrate is not limited. The substrate may have a single-layer structure or a multi-layer structure. The substrate may be a substrate comprising a conductive layer. The substrate may be a substrate including a base material and a conductive layer disposed on the base material. The substrate may be a substrate including a base material and a conductive layer in contact with the base material. The conductive layer may be disposed on one side of the substrate. The conductive layers may be disposed on both sides of the substrate. The substrate may comprise layers other than the conductive layer.

The substrate is preferably transparent. Examples of the substrate include glass, silicon, and resin films. The substrate is preferably a resin film. The substrate includes a radical plate having a single-layer structure.

Examples of the transparent glass include reinforced glass typified by gorilla glass of Corning Incorporated co. As the transparent glass, materials used in japanese patent application laid-open publication nos. 2010-86684 and 2010-152809 and 2010-257492 can also be used.

The resin film is preferably a resin film with small optical distortion or a resin film with high transparency. Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.

Examples of the conductive layer include a conductive layer used for a general circuit wiring and a touch panel wiring. The conductive layer is preferably an electrode pattern of a sensor corresponding to a visual recognition portion used in the capacitive touch panel or a wiring of a peripheral lead portion.

The conductive layer is preferably at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphite layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer, from the viewpoints of conductivity and fine wire formability.

Examples of the component of the conductive layer include a metal and a conductive layerAn electrical metal oxide. As the metal, al, zn, cu, fe, ni, cr, mo, ag and Au are exemplified. Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide: indium zinc Oxide), and SiO ₂ . In the present invention, "conductive" means that the volume resistivity is less than 1X 10 ⁶ Properties of Ω cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm。

The substrate may contain 1 or more than 2 conductive layers. When the substrate includes 2 or more conductive layers, the substrate preferably includes 2 or more conductive layers formed of mutually different materials. At least 1 of the 2 or more conductive layers preferably contains a conductive metal oxide.

(method for producing laminate)

The method of manufacturing the laminate is not limited. The laminate is formed, for example, by the method of forming each layer described above. The laminate is preferably formed using a photosensitive transfer material. For example, by bringing a photosensitive transfer material including a temporary support and a photosensitive layer in this order into contact with a transfer target (for example, a substrate), a laminate including the transfer target, the photosensitive layer, and the temporary support in this order can be formed. Further, by bringing the photosensitive transfer material including the temporary support and the resin-layer-level photosensitive layer in this order into contact with the transfer target (for example, a substrate), a laminate including the transfer target, the photosensitive layer, the resin layer, and the temporary support in this order can be formed. The method for producing the photosensitive transfer material and the method for using the same follow the items described in the item "photosensitive layer".

Use

The exposure method according to an embodiment of the present invention can be used for various processing techniques using photolithography, for example. As a use of the exposure method according to an embodiment of the present invention, for example, a method for producing a resin pattern is given. However, the application of the exposure method according to an embodiment of the present invention is not limited to the above application.

< method for producing resin Pattern >

The method for producing a resin pattern according to an embodiment of the present invention is a method for producing a resin pattern using the photomask according to an embodiment of the present invention. The method for producing a resin pattern according to an embodiment of the present invention preferably includes the steps of: a photomask according to an embodiment of the present invention (i.e., a "10 th preparation step") is prepared; contacting the photomask with the photosensitive layer, and exposing the photosensitive layer through the photomask (i.e., the "4 th exposure step"); and developing the exposed photosensitive layer to form a resin pattern (hereinafter, sometimes referred to as "development step 1"). Hereinafter, a method for manufacturing a resin pattern according to an embodiment of the present invention will be described in detail.

Preparation procedure 10

In the 10 th preparation step, a photomask according to an embodiment of the present invention is prepared. The photomask according to an embodiment of the present invention is as described in the above "photomask". In one embodiment, the photomask is preferably the photomask according to embodiment 1 described in the "photomask" item. In one embodiment, the photomask is preferably the photomask according to embodiment 2 described in the above "photomask".

4 th Exposure procedure

In the 4 th exposure step, a photomask is brought into contact with the photosensitive layer, and the photosensitive layer is exposed through the photomask. The 4 th exposure step is described in the above item "1 st exposure method". The preferred embodiment of the 4 th exposure step is the same as the preferred embodiment of the 4 th exposure step described in the above item "1 st exposure method".

Development procedure 1

In the 1 st development step, the exposed photosensitive layer is developed to form a resin pattern. Specifically, in the 1 st development step, the photosensitive layer is patterned by removing the exposed or unexposed portions of the photosensitive layer. For example, in the development of the positive photosensitive layer, the exposed portion of the positive photosensitive layer is removed. For example, in the development of the negative photosensitive layer, the non-exposed portion of the negative photosensitive layer is removed.

As a developing method of the photosensitive layer, for example, a method using a developing solution can be cited. In the 1 st developing step, a known developer can be used. Examples of the developer include a developer described in JP-A-5-72724. The developer is preferably an aqueous alkali developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05mol/L to 5 mol/L. The developer may contain a water-soluble organic solvent and/or a surfactant. As the developer, the developer described in paragraph 0194 of International publication No. 2015/093271 is also preferable.

The developing method is not limited. Examples of the development method include spin-coating immersion development, shower development, spin development, and immersion development. The shower development is a development process in which a developing solution is sprayed onto the photosensitive layer after exposure to remove the exposed portion or the unexposed portion of the photosensitive layer.

The temperature of the developer is not limited. The temperature of the developer is preferably 20 to 40 ℃.

After the resin pattern is formed, the cleaning agent is preferably sprayed by spraying, and the development residues are removed while wiping with a brush.

Modification of the invention

As in the exposure method according to an embodiment of the present invention, a laminate including a photosensitive layer and another layer may be used in the method for producing a resin pattern according to an embodiment of the present invention. Hereinafter, a method for producing a resin pattern using a laminate including a photosensitive layer and other layers will be described. Embodiments of the method for producing a resin pattern using a laminate including a photosensitive layer and other layers (for example, a contact method, an exposure condition, and a development method) follow the above-described matters except for the matters described below.

The method for producing a resin pattern according to an embodiment of the present invention preferably includes: 10 th preparation step, 11 th preparation step, 5 th exposure step, and 2 nd development step. In the 10 th preparation step, a photomask according to an embodiment of the present invention is prepared. In the 11 th preparation step, a laminate including a photosensitive layer and a temporary support in this order is prepared. In the 5 th exposure step, the photomask is brought into contact with the temporary support, and the photosensitive layer is exposed through the photomask and the temporary support. The 2 nd developing step preferably includes the steps of: the exposed photosensitive layer is developed to form a resin pattern. The method of exposing the photosensitive layer through the temporary support can suppress contamination of the photomask. In the above method for producing a resin pattern, the temporary support is preferably peeled off after the exposure of the photosensitive layer and before the development of the photosensitive layer.

The method for producing a resin pattern according to an embodiment of the present invention preferably includes: a 12 th preparation step, a 13 th preparation step, a 2 nd exposure step, a 6 th exposure step, and a 3 rd development step. In the 12 th preparation step, a photomask according to an embodiment of the present invention is prepared. In the 13 th preparation step, a laminate including a photosensitive layer and a temporary support in this order is prepared. In the 2 nd exposure step, the temporary support is peeled off to expose the surface of the photosensitive layer. In the 6 th exposure step, the photomask is brought into contact with the surface of the photosensitive layer exposed by the peeling of the temporary support, and the photosensitive layer is exposed through the photomask. In the 3 rd developing step, the exposed photosensitive layer is developed to form a resin pattern.

The laminate used in the method for producing a resin pattern may further include a resin layer between the photosensitive layer and the temporary support. When a laminate including a resin layer between a photosensitive layer and a temporary support is used, the photosensitive layer is exposed to light through a photomask and the resin layer in the 4 th exposure step. For example, when the photosensitive layer is exposed without peeling off the temporary support, the photosensitive layer is exposed through the photomask, the temporary support, and the resin layer. For example, when the photosensitive layer is exposed after the temporary support is peeled off, the photomask is brought into contact with the resin layer (specifically, the surface of the resin layer exposed by the peeling off of the temporary support), and the photosensitive layer is exposed through the photomask and the resin layer. The laminate used in the exposure method may include a substrate, a photosensitive layer, and a temporary support in this order.

The constituent elements and the manufacturing method of the laminate used in the method for manufacturing a resin pattern correspond to the constituent elements and the manufacturing method of the laminate described in the above item "exposure method". The preferred mode of the temporary support in the laminate used in the method for producing a resin pattern is the same as the preferred mode of the temporary support described in the above item of "exposure method". The preferred mode of the resin layer in the laminate used in the method for producing a resin pattern is the same as the preferred mode of the resin layer described in the above item of "exposure method". The preferred mode of the radical plate in the laminate used in the method for producing a resin pattern is the same as the preferred mode of the radical plate described in the above item of the "exposure method".

Use

Examples of the use of the method for producing a resin pattern according to an embodiment of the present invention include a method for producing a circuit wiring and a method for producing a permanent film. For example, according to the method for manufacturing a resin pattern according to an embodiment of the present invention, after a resin pattern is formed on a substrate including a conductive layer, the conductive layer not covered with the resin pattern is removed by etching, whereby a circuit wiring can be manufactured. The resin pattern obtained by the method for producing a resin pattern according to an embodiment of the present invention can be used as a permanent film. However, the application of the method for producing a resin pattern according to an embodiment of the present invention is not limited to the above application.

Examples

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. The contents (e.g., materials, processes, and conditions) of the examples shown below may be appropriately changed within the scope of the object of the present invention. In the examples shown below, "%" is based on mass unless otherwise specified.

< preparation of photosensitive composition A >

The following components were mixed with propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO k.k.) to obtain a mixture having a solid content of 10 mass%. The mixture was filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain a photosensitive composition A. The photosensitive composition a is a composition for forming a positive photosensitive layer.

Compositions containing polymer A-1: converted to 100 parts by mass of solid content

Photoacid generator B-1:3 parts by mass

Surfactant C-1:0.1 part by mass

Basic compound D-1:1.6 parts by mass

(preparation of a composition containing Polymer A-1)

Propylene glycol monomethyl ether acetate (75.0g,SHOWA DENKO K.K. Manufactured) was added to the 3-neck flask, and the temperature was raised to 90℃under a nitrogen atmosphere. To a 3-neck flask solution maintained at 90±2 ℃ for 2 hours, a solution containing 2-tetrahydrofuranyl acrylate (40.0 g, a synthesized product obtained by a method described later), acrylic acid (2.0g,Tokyo Chemical Industry Co..manufactured by ltd., ltd.), ethyl acrylate (20.0g,Tokyo Chemical Industry Co..manufactured by ltd., ltd.), methyl methacrylate (22.0g,Tokyo Chemical Industry Co..manufactured by ltd., ltd.), cyclohexyl acrylate (16.0 g), dimethyl 2,2' -azobis (2-methylpropionate) (4.0g,FUJIFILM Wako Pure Chemical Corporation manufactured by d.), and propylene glycol monomethyl ether acetate (75.0 g) was added dropwise. The resulting solution was stirred at 90.+ -. 2 ℃ for 2 hours to obtain a composition containing polymer A-1 (solid content: 40.0 mass%).

(Synthesis of 2-tetrahydrofuranyl acrylate)

Acrylic acid (72.1 g,1.0 mol), hexane (72.1 g) were added to a 3-neck flask, and cooled to 20 ℃. Camphorsulfonic acid (7.0 mg,0.03 mmol) and 2-dihydrofuran (77.9 g,1.0 mol) were added dropwise, followed by stirring at 20.+ -. 2 ℃ for 1.5 hours, then, heating to 35 ℃ and stirring for 2 hours. The suction filter was successively filled with KYOWARD200 (filter material, aluminum hydroxide powder, kyowa Chemical Industry co., ltd.) and KYOWARD1000 (filter material, hydrotalcite-based powder, kyowa Chemical Industry co., ltd.) and the reaction solution was filtered to obtain a filtrate. To the resulting filtrate, hydroquinone monomethyl ether (1.2 mg) was added, followed by concentration under reduced pressure at 40℃to thereby obtain 140.8g of 2-tetrahydrofuranyl acrylate (alias: tetrahydrofuranyl acrylate) (yield: 99.0%) as a colorless oil.

(photoacid generator B-1)

Photoacid generator B-1 is a compound having the following structure. Photoacid generator B-1 was synthesized according to the method described in paragraph 0204 of JP-A2013-47765.

[ chemical formula 5]

(surfactant C-1)

The surfactant C-1 is a compound having the following structure.

[ chemical formula 6]

(basic Compound D-1)

The basic compound D-1 is a compound having the following structure.

[ chemical formula 7]

< preparation of photosensitive composition B >

Photosensitive composition B was prepared by mixing the following components. The photosensitive composition B is a composition for forming a negative photosensitive layer.

Composition containing polymer B-1: 21.87 parts by mass in terms of solid content

Arofix M270 (TOAGOSEI co., ltd.): 0.51 part by mass

NK Ester BPE-500 (Shin-Nakamura Chemical Co., ltd.): 4.85 parts by mass

B-CIM (photo radical generator (photopolymerization initiator), manufactured by Hampford Co., ltd., 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer): 0.89 part by mass

NBCA (sensitizer, 10-butyl-2-chloroacridone, KUROGANE KASEI Co., manufactured by Ltd.): 0.05 part by mass

N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.02 part by mass

Phenazine (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.025 parts by mass

1-phenyl-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.001 part by mass

LCV (pigment, colorless crystal violet, manufactured by YAMADA CHEMICALCO., LTD.): 0.053 part by mass

VPB-NAPS (pigment, victoria pure blue-naphthalene sulfonate, hodogaya Chemical co., ltd.): 0.009 parts by mass

Methyl ethyl ketone (SANKYO chemistry co., ltd.): 30.87 parts by mass

Propylene glycol monomethyl ether acetate: 33.92 parts by mass

Tetrahydrofuran (Mitsubishi Chemical Corporation manufacture): 6.93 parts by mass

(preparation of a composition containing Polymer B-1)

Propylene glycol monomethyl ether acetate (116.5 parts by mass) was placed in a 3-neck flask, and the temperature was raised to 90℃under a nitrogen atmosphere. To a 3-neck flask solution maintained at 90±2 ℃ was added dropwise a solution containing styrene (52.0 parts by mass, manufactured by FUJIFILM Wako Pure Chemical Corporation), methyl methacrylate (19.0 parts by mass), methacrylic acid (29.0 parts by mass, tokyo Chemical Industry co., manufactured by ltd.) dimethyl 2,2' -azobis (2-methylpropionate) (4.0 parts by mass) and propylene glycol monomethyl ether acetate (116.5 parts by mass) over a period of 2 hours. After completion of the dropwise addition, the mixture was stirred at 90.+ -. 2 ℃ for 2 hours, whereby a composition containing polymer B-1 (solid content: 30.0 mass%) was obtained.

< preparation of resin compositions C to E >

Resin composition C, resin composition D, and resin composition E were prepared by mixing the following components. The unit of the amount of the components shown below is parts by mass.

TABLE 1

< measurement of general hardness of photosensitive layer and resin layer >

The photosensitive composition was applied to a film of cosmosfine a4300 (PET film having a thickness of 50 μm, toyobo co., ltd.) using a bar coater so that the dry film thickness became 2 μm. The coated photosensitive composition was dried at 100 ℃ for 10 minutes using an oven, thereby forming a photosensitive layer. A spherical indenter (diameter: 0.4 mm) was attached to an HM2000 type durometer manufactured by FISCHER INSTRUMENTS K.K., and a press-in test was performed at 23℃and 50% RH (relative humidity). The press-in test was performed until the maximum load was reached while the load was increased stepwise. In the press-in test, the loading time was set to 10 seconds, and the creep time was set to 5 seconds. The universal hardness (unit: N/mm) of the photosensitive layer was obtained from the test load when the surface area of the spherical indenter in contact with the photosensitive layer and the press-in depth became 1/10 of the thickness of the photosensitive layer before the test ² ). The 10-time press-in test was repeated to obtain an arithmetic average of general hardness of the photosensitive layer. The general hardness of the resin layer was measured by the same method as the method for measuring the general hardness of the photosensitive layer except that the photosensitive composition was changed to the resin composition. The measurement results are shown in tables 3 to 4.

< preparation of photomask-1 >

Photomask-1 was fabricated by the following method. A chromium thin film (light shielding layer, thickness: 170 nm) was formed on a quartz substrate (transparent support, length: 100mm, width: 100mm, thickness: 2.8 mm) by sputtering. The chromium thin film is patterned by photolithography to form a pattern (light shielding layer) of the chromium thin film. In photolithography, specifically, a pattern of a chromium thin film is formed by exposing and developing a photosensitive layer disposed on the chromium thin film, etching the chromium thin film, and removing a resin pattern. The photomask-1 includes a quartz substrate and a pattern of a chromium thin film disposed on the quartz substrate. Photomask-1 had a line-to-space pattern with a line width of 8 μm (Duty ratio=1:1).

< preparation of photomask-2 >

Photomask-2 was fabricated by the following method. The following composition for forming a protective layer-1 was applied on the pattern of the quartz substrate and the chromium thin film of the photomask-1 manufactured by the manufacturing method of the photomask-1 by a spin coater to form a protective layer having a thickness of 2.5. Mu.m. The photomask-2 thus obtained comprises a quartz substrate, a pattern of a chromium film disposed on the quartz substrate, and a protective layer disposed on the pattern of the quartz substrate and the pattern of the chromium film. Photomask-2 had a line-to-space pattern with a line width of 8 μm (Duty ratio=1:1).

(composition for Forming protective layer-1)

The protective layer-forming composition-1 contains the following components.

Blocked polyisocyanate hardener (Duranate TPA-100,ASAHI KASEI CORPORATION): 0.74 part by mass

Acrylic polyol resin (ACRYDIC A-807,DIC Corporation): 3.19 parts by mass

Methyl ethyl ketone: 3.05 parts by mass

Ethyl acetate: 3.05 parts by mass

< preparation of photomask-3 >

Photomask-3 was fabricated by the following method. In a reaction vessel made of quartz, the pattern of the quartz substrate and the chromium thin film of the photomask-1 manufactured by the manufacturing method of the photomask-1 was brought into contact with the vapor of (heptadecafluoro-1, 2-tetrahydrodecyl) -1-triethoxysilane at room temperature for 50 minutes. Photomask-1 was heated at 100℃for 30 minutes to form a protective layer. The photomask-3 thus obtained comprises a quartz substrate, a pattern of a chromium film disposed on the quartz substrate, and a protective layer disposed on the pattern of the quartz substrate and the pattern of the chromium film. Photomask-3 had a line-to-space pattern with a line width of 8 μm (Duty ratio=1:1).

< examples 1 to 10 and comparative examples 1 to 6>

The surface roughness of the photomask was adjusted by performing wet blasting treatment on the photomask as described in tables 2 and 3. Hereinafter, specific steps of the wet blasting treatment will be described. A spray nozzle having a width of 32cm was provided at a position where slurry containing abrasive and water could be sprayed in the direction of gravity. The surfaces of the chromium thin films and the surfaces of the quartz substrates not covered with the chromium thin films (i.e., the 1 st surface of the transparent support) were subjected to wet blasting by passing the photomask through the slurry sprayed in the gravity direction by compressed air under the conditions of the wet blasting shown in tables 2 and 3. The conveying speed of the photomask in the wet blasting treatment was set to 10 mm/sec. The following evaluation was performed using a photomask subjected to wet blasting. In table 3, the following evaluation was performed using a photomask not subjected to the blasting treatment for examples and comparative examples in which "-" is recorded in the column of "conditions of wet blasting treatment".

(evaluation of adhesion)

A photosensitive composition selected as described in table 3 was applied to a highly smooth surface of an A4-size polyethylene terephthalate (PET) film (cosmosine a4100, thickness: 100 μm, toyobo co., ltd.) using a bar coater so that the dry film thickness became 3 μm. The coated photosensitive composition was dried at 100 ℃ for 10 minutes using an oven, thereby forming a photosensitive layer. The laminate comprising the PET film and the photosensitive layer was kept at 23℃and 50% (relative humidity) for 1 hour, and then cut into 10cm by 10cm dimensions. The photomask is brought into contact with the photosensitive layer of the laminate, and at least a chromium thin film and a quartz substrate are sequentially disposed on the photosensitive layer. A load of 84kg was applied to the photomask and the laminate at 30℃and 80% (relative humidity) for 21 hours. Based on the feel of the laminate when peeled from the photomask and the appearance of the photomask after the laminate was peeled from the photomask, the adhesiveness of the photomask to the photosensitive layer was evaluated according to the following criteria. The evaluation results are shown in table 3.

Reference-

A: when the laminate is peeled off from the photomask, the laminate is not sensitive to adhesion of the photomask, and there is no adhesion trace of the photosensitive layer on the photomask.

B: when the laminate is peeled off from the photomask, the laminate is sensitive to adhesion to the photomask, and there is no adhesion trace of the photosensitive layer on the photomask.

C: when the laminate is peeled off from the photomask, the laminate is sensitive to adhesion to the photomask, and the photomask has adhesion marks of the photosensitive layer.

D: when the laminate is peeled off from the photomask, the laminate has a sense of adhesion to the photomask, and 30% or more of the area of the photosensitive layer is transferred to the photomask.

(evaluation of linearity)

The photosensitive composition selected as described in Table 3 was applied to A4-size PET film (thickness: 100 μm) by a bar coater so that the dry film thickness became 3. Mu.m. The coated photosensitive composition was dried at 100 ℃ for 10 minutes using an oven, thereby forming a photosensitive layer. A photomask having a line and space pattern (Duty ratio 1:1) with a line width of 8 μm was brought into contact with the photosensitive layer, and at least a chromium film and a quartz substrate were disposed in this order on the photosensitive layer. The photosensitive layer was exposed to light through a photomask using an extra-high pressure mercury lamp. The photosensitive layer is developed to form a resin pattern. Development was performed by spray development using a 1.0% aqueous sodium carbonate solution at 25 ℃ for 30 seconds. The resin pattern was observed with an optical microscope, and the line width at 20 points arbitrarily selected in the resin pattern was measured. The standard deviation σ was obtained from the measured value, and a value 3 times the standard deviation σ was defined as LWR (Line Width Roughness: line width roughness) and used as an index of the linearity of the resin pattern. Based on the LWR value, the resin pattern was evaluated for linearity according to the following criteria. The evaluation results are shown in table 3.

Reference-

A：LWR<250nm

B：250nm<LWR≤500nm

C：500nm<LWR

< examples 11 to 18 and comparative examples 7 to 10>

The surface roughness of the photomask was adjusted by performing wet blasting treatment on the photomask as described in tables 2 and 4. The specific steps of the wet blasting treatment are as described. The following evaluation was performed using a photomask subjected to wet blasting. In table 4, the following evaluation was performed using a photomask not subjected to the blasting treatment for examples and comparative examples in which "-" is shown in the column of "conditions of wet blasting treatment".

(evaluation of adhesion and linearity)

Using a bar coater, a polyethylene terephthalate (PET) film (LUMIRROR 16KS40,Toray Industries,Inc, thickness: 16 μm) of A4 size was coated with a resin composition selected as described in tables 2 and 4 so that the dry film thickness became the values described in table 4. The coated resin composition was dried at 100 ℃ for 10 minutes using an oven, thereby forming a resin layer. The photosensitive composition B was applied to the resin layer by a bar coater so that the dry film thickness became 3 μm. The coated photosensitive composition was dried at 100 ℃ for 10 minutes using an oven, thereby forming a photosensitive layer. The photosensitive transfer material including the PET film (temporary support), the resin layer, and the photosensitive layer in this order was obtained through the above steps.

A copper layer (thickness: 200 nm) was formed on a polyethylene terephthalate (PET) film (thickness: 100 μm) by a sputtering method to obtain a PET substrate with a copper layer.

The photosensitive transfer material was laminated on a copper-clad PET substrate under lamination conditions of a roll temperature of 100 ℃, a line pressure of 1.OMPa, and a line speed of 4.0 m/min. The obtained laminate comprises a PT film, a copper layer, a photosensitive layer, a resin layer and a temporary support in this order. After peeling the PET film as the temporary support, the same evaluation as that of example 1 was performed. The evaluation results are shown in table 4.

TABLE 2

TABLE 3

TABLE 4

In tables 3 to 4, "surface roughness of chromium thin film", "surface roughness of quartz substrate" and "surface roughness of protective layer" were measured by the methods described above. For examples and comparative examples using a photomask subjected to wet blasting, surface roughness was measured using a photomask subjected to wet blasting. The "surface roughness of the quartz substrate" means the surface roughness of the portion of the surface of the quartz substrate on the chromium film side that is not covered with the chromium film. That is, the "surface roughness of the quartz substrate" means the surface roughness of the exposed portion of the 1 st surface of the transparent support defined in the present invention.

In tables 3 to 4, "haze" indicates haze of a light transmitting portion of a photomask (i.e., a portion of a quartz substrate not covered with a chromium film). The smaller the haze, the more suppressed the scattering of light. The haze was measured by using a haze measuring apparatus (trade name: "NDH-5000W", manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) in accordance with "JIS K7136". Haze was measured using a photomask subjected to wet blasting for examples and comparative examples in which a photomask subjected to wet blasting was used.

It is found that in examples 1 to 10, the adhesiveness of the photomask to the photosensitive layer was reduced, and a resin pattern having excellent linearity was formed, as compared with comparative examples 1 to 6. It is found that in examples 11 to 18, the adhesiveness of the photomask to the resin layer was reduced, and a resin pattern having excellent linearity was formed, as compared with comparative examples 7 to 10.

The disclosure of japanese patent application 2020-145976, filed on 8/31/2020, is incorporated herein by reference in its entirety.

All documents, patent applications and technical standards described in this specification are incorporated by reference into this specification to the same extent as if each document, patent application and technical standard was specifically and individually described to be incorporated by reference.

Claims

1. A photomask, comprising:

a transparent support having a 1 st surface and a 2 nd surface on the opposite side of the 1 st surface; and

A light shielding layer disposed on a part of the 1 st surface of the transparent support,

the surface roughness Rz of the exposed part of the 1 st surface is 0.1-0.5 mu m,

the surface roughness Rz of the light shielding layer is 0.1-0.5 mu m.

2. The photomask of claim 1, wherein,

the surface roughness Ra of the exposed part of the 1 st surface is 5-50 nm, and the surface roughness Ra of the light shielding layer is 5-50 nm.

3. A photomask, comprising:

a transparent support having a 1 st surface and a 2 nd surface on the opposite side of the 1 st surface;

a light shielding layer disposed on a part of the 1 st surface of the transparent support; and

A protective layer disposed on the 1 st surface of the transparent support and the light shielding layer,

the surface roughness Rz of the protective layer is 0.1-0.5 mu m.

4. The photomask of claim 3, wherein,

the surface roughness Ra of the protective layer is 5 nm-50 nm.

5. The photomask of claim 3 or 4, wherein,

the protective layer contains an organic polymer compound.

6. The photomask of claim 5, wherein,

the organic polymer compound contains a structural unit derived from urethane acrylate.

7. The photomask of any of claims 3 to 6, wherein,

the protective layer contains a fluorine atom-containing compound.

8. The photomask of any of claims 1 to 7, wherein,

the transparent support is a tabular quartz glass.

9. The photomask of any of claims 1 to 8, wherein,

the light-shielding layer contains chromium.

10. An exposure method comprising the steps of:

preparing the photomask of any of claims 1 to 9; and

The photomask is brought into contact with the photosensitive layer, and the photosensitive layer is exposed to light with the photomask interposed therebetween.

11. A method for manufacturing a resin pattern, comprising the steps of:

preparing the photomask of any of claims 1 to 9;

contacting the photomask with the photosensitive layer and exposing the photosensitive layer with the photomask in between; and

And developing the exposed photosensitive layer to form a resin pattern.

12. A method for manufacturing a resin pattern, comprising the steps of:

Preparing the photomask of any of claims 1 to 9;

preparing a laminate comprising a photosensitive layer and a temporary support in this order;

contacting the photomask with the temporary support and exposing the photosensitive layer with the photomask and the temporary support therebetween; and

And developing the exposed photosensitive layer to form a resin pattern.

13. A method for manufacturing a resin pattern, comprising the steps of:

preparing the photomask of any of claims 1 to 9;

peeling the temporary support to expose the surface of the photosensitive layer;

contacting the photomask with the surface of the photosensitive layer exposed by the peeling of the temporary support, and exposing the photosensitive layer with the photomask interposed therebetween; and

And developing the exposed photosensitive layer to form a resin pattern.

14. The method for producing a resin pattern according to claim 12 or 13, wherein,

the laminate further comprises a resin layer between the photosensitive layer and the temporary support, and the resin layer has a universal hardness of 5.0N/mm as measured by a test load when the press-in depth is 1/10 of the thickness of the resin layer in a press-in test ² In the step of exposing the photosensitive layer, the photosensitive layer is exposed with the photomask and the resin layer interposed therebetween.

15. The method for producing a resin pattern according to claim 14, wherein,

the resin layer contains polyvinyl alcohol.

16. The method for producing a resin pattern according to any one of claims 11 to 15, wherein,

the general hardness of the photosensitive layer measured according to the test load when the press-in depth is 1/10 of the thickness of the photosensitive layer in the press-in test was 5.0N/mm ² The above.

17. A method for manufacturing a photomask, comprising the steps of:

preparing a laminate including a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface, and a light shielding layer disposed on a part of the 1 st surface of the transparent support; and

The laminate is subjected to sandblasting treatment, whereby the surface roughness Rz of the exposed portion of the 1 st surface is adjusted to 0.1 to 0.5 [ mu ] m, and the surface roughness Rz of the light shielding layer is adjusted to 0.1 to 0.5 [ mu ] m.

18. A method for manufacturing a photomask, comprising the steps of:

Preparing a laminate including a transparent support having a 1 st surface and a 2 nd surface opposite to the 1 st surface, a light shielding layer disposed on a part of the 1 st surface of the transparent support, and a protective layer disposed on the 1 st surface of the transparent support and the light shielding layer; and

The surface roughness Rz of the protective layer is adjusted to 0.1-0.5 [ mu ] m by performing sand blasting on the laminate.

19. The method for manufacturing a photomask according to claim 17 or 18, wherein,

the blasting is wet blasting.