CN116324619A - Information providing method, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel - Google Patents

Abstract

The present invention provides an information providing method for providing identifiable information to a photosensitive resin layer on which a latent image of a resin pattern is formed by exposure to light having a dominant wavelength λa, the information providing method comprising the steps of: irradiating a photosensitive resin layer containing a fluorescent material precursor with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material; and irradiating a region of the photosensitive resin layer exposed to light of the dominant wavelength λb with light of a dominant wavelength λc, wherein the dominant wavelength λa and the dominant wavelength λb satisfy a relationship of λa and λb, the dominant wavelength λa and the dominant wavelength λc satisfy a relationship of λc > λa, and the dominant wavelength λb and the dominant wavelength λc satisfy a relationship of λc > λb.

Description

Information providing method, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel

Technical Field

The present invention relates to an information providing method, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

Background

A substance having photosensitivity is used for example for identifying an article. For example, patent document 1 below discloses an image forming element including a composition having sensitivity to chemical radiation of 1 st wavelength, in which a photoluminescent label is arranged in the element, the label being responsive to radiation of 2 nd wavelength different from the 1 st wavelength. Patent document 1 discloses a method for producing a recording element, which includes the steps of: a) Providing an image forming element including a layer of a composition having sensitivity to chemical radiation of a 1 st wavelength, wherein a photoluminescent label is disposed within the element, the label exhibiting a response to radiation of a 2 nd wavelength different from the 1 st wavelength; b) Exposing the image forming element with the chemical radiation; and c) a step of processing the elements of step b) to form recording elements.

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2006-215545

Disclosure of Invention

Technical problem to be solved by the invention

The photosensitive resin layer used for photolithography can be formed into a resin pattern by exposure and development. The resin pattern is used, for example, as a permanent film or a protective film in etching treatment. For example, in the method for manufacturing the circuit wiring, after the resin pattern is formed on the conductive layer, the conductive layer not covered with the resin pattern is removed by etching treatment, so that the desired circuit wiring can be formed. In a pattern forming technique such as a circuit wiring manufacturing method, a pattern (hereinafter, referred to as a "pattern for recognition") indicating information such as a manufacturing lot number and a manufacturing date may be formed separately from a target pattern. The identification pattern is formed in a clearly visualized state. On the other hand, for the purpose of preventing information leakage, etc., a method of forming a visualized pattern by a specific process, which is generally invisible, is demanded as secret information. In the technique disclosed in patent document 1, a photoluminescent tag that exhibits response to radiation of a specific wavelength is used, but the technique described above is not suitable for application to a photosensitive resin layer to which desired confidential information is to be given.

An object of an embodiment of the present invention is to provide an information providing method including providing invisible information and visualization of the invisible information to a photosensitive resin layer.

Another object of another embodiment of the present invention is to provide a method for producing a resin pattern, which includes imparting invisible information and visualization of the invisible information to a photosensitive resin layer.

Another object of another embodiment of the present invention is to provide a method for manufacturing a circuit wiring, including imparting invisible information and visualization of the invisible information to a photosensitive resin layer.

Another object of another embodiment of the present invention is to provide a method for manufacturing a touch panel, including imparting invisible information and visualization of the invisible information to a photosensitive resin layer.

Means for solving the technical problems

<1> an information providing method for providing identifiable information to a photosensitive resin layer on which a latent image of a resin pattern is formed by exposure to light having a dominant wavelength λa, the information providing method comprising the steps of: irradiating a photosensitive resin layer containing a fluorescent material precursor with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material; and irradiating a region of the photosensitive resin layer exposed to light of the dominant wavelength λb with light of a dominant wavelength λc, wherein the dominant wavelength λa and the dominant wavelength λb satisfy a relationship of λa and λb, wherein the dominant wavelength λa and the dominant wavelength λc satisfy a relationship of λc > λa, and wherein the dominant wavelength λb and the dominant wavelength λc satisfy a relationship of λc > λb.

<2> the information providing method according to <1>, wherein,

observing the fluorescence includes observing the fluorescence through a filter that blocks the dominant wavelength λc.

<3> the information providing method according to <1> or <2>, wherein,

the dominant wavelength λa and the dominant wavelength λb satisfy a relationship of λb > λa.

<4> the information giving method according to any one of <1> to <3>, wherein,

the dominant wavelength λa is less than 400nm, the dominant wavelength λb is 400nm or more and less than 500nm, and the dominant wavelength λc is 500nm or more and less than 700nm.

<5> the information giving method according to any one of <1> to <4>, wherein,

the fluorescent material precursor is a compound having a triarylmethane structure.

<6> the information giving method according to any one of <1> to <5>, wherein,

the fluorescent material precursor is a leuco dye.

<7> the information giving method according to any one of <1> to <6>, wherein,

the photosensitive resin layer contains a polymer, a polymerizable compound, and a polymerization initiator.

<8> a method for manufacturing a resin pattern, comprising the steps of:

preparing a laminate comprising a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order; irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of a resin pattern; irradiating the photosensitive resin layer with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material; irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having a dominant wavelength λc, and observing fluorescence emitted from the fluorescent material; and developing the photosensitive resin layer to form a resin pattern, wherein the dominant wavelength λa and the dominant wavelength λb satisfy a relationship of λa+.λb, the dominant wavelength λa and the dominant wavelength λc satisfy a relationship of λc > λa, and the dominant wavelength λb and the dominant wavelength λc satisfy a relationship of λc > λb.

<9> a method for manufacturing a circuit wiring, comprising the steps of:

preparing a laminate comprising a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order; irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of a resin pattern; irradiating the photosensitive resin layer with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material; irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having a dominant wavelength λc, and observing fluorescence emitted from the fluorescent material; developing the photosensitive resin layer to form a resin pattern; and etching the conductive layer in a region where the resin pattern is not arranged to form a circuit wiring, wherein the dominant wavelength λa and the dominant wavelength λb satisfy a relationship of λa++λb, the dominant wavelength λa and the dominant wavelength λc satisfy a relationship of λc > λa, and the dominant wavelength λb and the dominant wavelength λc satisfy a relationship of λc > λb.

<10 > a method for manufacturing a touch panel, comprising the steps of:

preparing a laminate comprising a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order; irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of a resin pattern; irradiating the photosensitive resin layer with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material; irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having a dominant wavelength λc, and observing fluorescence emitted from the fluorescent material; developing the photosensitive resin layer to form a resin pattern; and etching the conductive layer in a region where the resin pattern is not arranged to form a wiring for a touch panel, wherein the dominant wavelength λa and the dominant wavelength λb satisfy a relationship of λa and λb, wherein the dominant wavelength λa and the dominant wavelength λc satisfy a relationship of λc > λa, and wherein the dominant wavelength λb and the dominant wavelength λc satisfy a relationship of λc > λb.

Effects of the invention

According to an embodiment of the present invention, there is provided an information providing method including providing invisible information and visualization of the invisible information to a photosensitive resin layer.

According to another embodiment of the present invention, there is provided a method for producing a resin pattern, including imparting invisible information and visualization of the invisible information to a photosensitive resin layer.

According to another embodiment of the present invention, there is provided a method for manufacturing a circuit wiring, including imparting invisible information and visualization of the invisible information to a photosensitive resin layer.

According to another embodiment of the present invention, there is provided a method for manufacturing a touch panel, including imparting invisible information and visualization of the invisible information to a photosensitive resin layer.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. 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 present invention, the numerical range indicated by the term "to" means a range in which numerical values before and after the term "to" are included as a lower limit value and an upper limit value, respectively. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value described in the embodiment.

In the present invention, the term "process" includes not only an independent process but also the term if the process is not clearly distinguished from other processes, as long as the desired purpose of the process is achieved.

In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, when a plurality of substances corresponding to a certain component are present in a composition, unless otherwise specified, the amount of the above component in the composition refers to the total amount of the plurality of the above substances present in the composition.

In the present invention, a combination of 2 or more preferred modes is a more preferred mode.

In the present invention, ordinal words (for example, "first" and "second") are terms used to distinguish a plurality of constituent elements, and do not limit the number of constituent elements or the merits of the constituent elements.

In the present invention, the unsubstituted and substituted groups (atomic groups) include groups having a substituent and groups having no substituent. For example, the label of "alkyl" includes an alkyl group having a substituent (a substituted alkyl group) and an alkyl group having no substituent (an unsubstituted alkyl group).

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

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

In the present invention, "(meth) acrylate" means an acrylate or a methacrylate.

In the present invention, "(meth) acryl" means acryl or methacryl.

In the present invention, unless otherwise specified, "exposure" includes not only exposure with light but also drawing with a particle beam using an electron beam and an ion beam. Examples of the light used for exposure include an open spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser light, extreme ultraviolet (EUV (Extreme ultraviolet lithography: extreme ultraviolet lithography) light), and activating rays (active energy rays) such as X-rays.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights obtained by detecting a compound in Tetrahydrofuran (THF) by a differential refractometer using a gel permeation chromatography (GPC: gel Permeation Chromatography) analysis apparatus using columns of TSKgel GMHxL (TOSOH CORPORATION), TSKgel G4000HxL (TOSOH CORPORATION) and TSKgel G2000HxL (TOSOH CORPORATION) and converting the compounds into a standard substance using polystyrene.

In the present invention, "solid component" means a component other than a solvent. The liquid component which does not belong to the solvent is contained in the "solid component".

< method for providing information >

The information providing method according to an embodiment of the present invention is a method of providing identifiable information to a photosensitive resin layer on which a latent image of a resin pattern is formed by exposure to light having a dominant wavelength λa. The information providing method includes the steps of: irradiating the photosensitive resin layer containing the fluorescent material precursor with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material (hereinafter, sometimes referred to as a "conversion step a"); and irradiating a region of the photosensitive resin layer exposed to light of the dominant wavelength λb with light of the dominant wavelength λc to observe fluorescence emitted from the fluorescent material (hereinafter, sometimes referred to as "observation step a"). Further, in the above-described information providing method, the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa++λb, the dominant wavelength λa and the dominant wavelength λc satisfy the relationship λc > λa, and the dominant wavelength λb and the dominant wavelength λc satisfy the relationship λc > λb.

In the conversion step a, the fluorescent material precursor contained in the photosensitive resin layer is converted into a fluorescent material by exposure to light having a dominant wavelength λb. The region containing the fluorescent material is completely or hardly visually recognized unless it is exposed to light of the dominant wavelength λc. By adjusting the irradiation region of the light having the dominant wavelength λb according to the target information, invisible information can be given to the photosensitive resin layer. Examples of the invisible information include characters, graphics, and symbols. However, the invisible information is not limited to the specific examples described above. For example, by adjusting the irradiation region of light having the dominant wavelength λb according to the shape of the number indicating the manufacturing date, the manufacturing date as invisible information can be formed on the photosensitive resin layer. Next, in the observation step a, the fluorescent material is excited by light having a dominant wavelength λc to emit fluorescence. By utilizing the luminescence of the fluorescent material, invisible information can be visualized only when necessary. Further, since the dominant wavelength λb is different from the dominant wavelength λa and the dominant wavelength λc is larger than the dominant wavelength λa and the dominant wavelength λb, unexpected reaction (for example, formation of a latent image of the resin pattern) in the photosensitive resin layer during irradiation of the light of the dominant wavelength λb and the light of the dominant wavelength λc can be suppressed, and addition of invisible information and visualization of invisible information can be performed. Therefore, according to the above-described embodiment, it is possible to provide an information imparting method including imparting invisible information to the photosensitive resin layer and visualizing the invisible information.

Main wavelength

Hereinafter, the dominant wavelength will be described. In the present invention, the "dominant wavelength" refers to a peak wavelength in a spectral distribution of light irradiated to an object. The "peak wavelength" refers to a wavelength having the highest intensity among the spectral distributions of light. However, in the case where the spectral distribution includes a plurality of peak wavelengths, 1 peak wavelength required for causing the target reaction is regarded as a dominant wavelength. For example, when light having a peak wavelength of 365nm (i-ray), 405nm (h-ray) and 436nm (g-ray) is irradiated to a photosensitive resin layer having sensitivity to 365nm light and containing a component that causes photopolymerization by 365nm light, 365nm is regarded as a dominant wavelength. For example, when light is irradiated to the photosensitive resin layer through a filter that transmits only light in the vicinity of 405nm, which is disposed between the high-pressure mercury lamp and the photosensitive resin layer, the dominant wavelength is 405nm. For example, when only 405nm of light is irradiated to the photosensitive resin layer by a light source such as a laser or a light emitting diode, the dominant wavelength is 405nm. The dominant wavelength is measured by a known measuring device capable of measuring the spectral distribution.

The dominant wavelength λa is a wavelength used to form a latent image of the resin pattern on the photosensitive resin layer. The latent image of the resin pattern is defined by the exposed portions and the non-exposed portions. In a photosensitive resin layer on which a latent image of a resin pattern is formed by exposure with light having a dominant wavelength λa, a difference occurs between the solubility of the exposed portion in a developer and the solubility of the unexposed portion in the developer. For example, in the negative photosensitive resin layer, the solubility of the exposed portion to the developer is lower than the solubility of the non-exposed portion to the developer. By developing the negative photosensitive resin layer on which the latent image of the resin pattern is formed, the non-exposed portion is removed, and the exposed portion forms the resin pattern. On the other hand, in the positive photosensitive resin layer, the solubility of the exposed portion to the developer is higher than the solubility of the non-exposed portion to the developer. By developing the positive photosensitive resin layer on which the latent image of the resin pattern is formed, the exposed portion is removed, and the non-exposed portion forms the resin pattern. That is, the shape of the exposed portion of the negative photosensitive resin layer corresponds to the shape of the resin pattern formed by development, and the shape of the non-exposed portion of the positive photosensitive resin layer corresponds to the shape of the resin pattern formed by development.

The dominant wavelength λb is the wavelength used to convert the fluorescent material precursor into the fluorescent material. The conversion process from the fluorescent material precursor to the fluorescent material is, for example, accompanied by a change in the chemical structure of the fluorescent material precursor (e.g., cleavage of a chemical bond).

The dominant wavelength λc is a wavelength for exciting the fluorescent material to release fluorescence.

In the information providing method according to an embodiment of the present invention, the dominant wavelength λa, dominant wavelength λb, and dominant wavelength λc satisfy the following relations (1) to (3).

(1) The dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa+.λb.

(2) The dominant wavelength λa and the dominant wavelength λc satisfy the relationship of λc > λa.

(3) The dominant wavelength λb and the dominant wavelength λc satisfy the relationship of λc > λb.

In the information providing method according to an embodiment of the present invention, by satisfying the relation of the dominant wavelength λa and the dominant wavelength λb as λa+.λb, unexpected reaction (for example, formation of a latent image of a resin pattern) in the photosensitive resin layer during irradiation of light of the dominant wavelength λb can be suppressed, and desired invisible information can be provided to the photosensitive resin layer.

In one embodiment, the dominant wavelength λa and dominant wavelength λb preferably satisfy the relationship λb > λa. In the case of forming a latent image of a resin pattern on a photosensitive resin layer, light having a short wavelength is generally used as light having energy necessary for initiating a reaction contributing to formation of the latent image. By satisfying the relationship that λb > λa by the dominant wavelength λa and the dominant wavelength λb, for example, the energy of the light of the dominant wavelength λb is lower than the energy of the light of the dominant wavelength λa. Therefore, an unexpected reaction (for example, formation of a latent image of the resin pattern) in the photosensitive resin layer during irradiation of the light having the dominant wavelength λb can be further suppressed.

In one embodiment, the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λb is preferably 10nm or more, more preferably 20nm or more, still more preferably 30nm or more, and particularly preferably 35nm or more. By increasing the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λb, an unexpected reaction (for example, formation of a latent image of a resin pattern) in the photosensitive resin layer during irradiation of light of the dominant wavelength λb can be further suppressed. The upper limit of the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λb is determined, for example, in a range where the dominant wavelength λa, the dominant wavelength λb, and the dominant wavelength λc satisfy the above-described relations (1) to (3). The upper limit of the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λb may also be 100nm, 80nm, 50nm, 45nm or 40nm. The absolute value of the difference between the dominant wavelength λa and the dominant wavelength λb is preferably 10nm to 100nm, more preferably 20nm to 50nm, and further preferably 30nm to 45nm. Further, it is preferable that the dominant wavelength λa and dominant wavelength λb satisfy the relation of Nb > λa and that the absolute value of the difference between the dominant wavelength λa and dominant wavelength λb satisfies the above-described range.

In the information providing method according to the embodiment of the present invention, the dominant wavelength λa and the dominant wavelength λc satisfy the relationship of λc > λa and the dominant wavelength λb and the dominant wavelength λc satisfy the relationship of λc > λb, in other words, the dominant wavelength λc is larger than the dominant wavelength λa and the dominant wavelength λb, whereby unexpected reaction (for example, formation of a latent image of a resin pattern) in the photosensitive resin layer during irradiation of light of the dominant wavelength λc can be suppressed.

In one embodiment, the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λc is preferably 100nm or more, more preferably 120nm or more, and still more preferably 150nm or more. By increasing the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λc, an unexpected reaction (for example, formation of a latent image of a resin pattern) in the photosensitive resin layer during irradiation of light of the dominant wavelength λc can be further suppressed. The upper limit of the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λc is determined, for example, in a range where the dominant wavelength λa, the dominant wavelength λb, and the dominant wavelength λc satisfy the above-described relations (1) to (3). The upper limit of the absolute value of the difference between the dominant wavelength λa and the dominant wavelength λc may be 300nm, 250nm or 200nm. The absolute value of the difference between the dominant wavelength λa and the dominant wavelength λc is preferably 10nm to 300nm, more preferably 120nm to 300nm, and further preferably 150nm to 250nm.

In one embodiment, the absolute value of the difference between the dominant wavelength λb and the dominant wavelength λc is preferably 20nm or more, more preferably 60nm or more, and still more preferably 100nm or more. By increasing the absolute value of the difference between the dominant wavelength λb and the dominant wavelength λc, an unexpected reaction (for example, conversion from a fluorescent material precursor to a fluorescent material) can be suppressed from occurring in the photosensitive resin layer during irradiation of the light of the dominant wavelength λc. The upper limit of the absolute value of the difference between the dominant wavelength λb and the dominant wavelength λc is determined, for example, in the range where the dominant wavelength λa, the dominant wavelength λb, and the dominant wavelength λc satisfy the above-described relations (1) to (3). The upper limit of the absolute value of the difference between the dominant wavelength lambdab and the dominant wavelength lambdac may also be 250nm, 200nm or 150nm. The absolute value of the difference between the dominant wavelength λb and the dominant wavelength λc is preferably 20nm to 250nm, more preferably 60nm to 200nm, and still more preferably 100nm to 150nm.

The dominant wavelength λa is preferably less than 410nm, more preferably less than 400nm. The upper limit of the dominant wavelength λa may also be 390nm, 380nm or 370nm. Regarding the lower limit of the dominant wavelength λa, there is no limitation. The lower limit of the dominant wavelength λa may also be 190nm, 230nm, 300nm or 350nm. The dominant wavelength λa is preferably 300nm or more and less than 400nm, more preferably 350nm or more and less than 400nm.

The dominant wavelength λb is preferably 390nm or more, more preferably 400nm or more. The lower limit of the dominant wavelength lambdab may also be 405nm. The dominant wavelength lambdab is preferably less than 500nm. The upper limit of the dominant wavelength λb may also be 480nm, 450nm or 410nm. The dominant wavelength λb is preferably 400nm or more and less than 500nm.

The dominant wavelength λc is preferably 500nm or more. The lower limit of the dominant wavelength lambdac may also be 510nm or 520nm. The dominant wavelength lambdac is preferably less than 700nm. The upper limit of the dominant wavelength λc may also be 600nm or 550nm. The dominant wavelength λc is preferably 500nm or more and less than 700nm.

In one embodiment, the dominant wavelength λa is preferably less than 410nm, the dominant wavelength λb is 410nm or more and less than 500nm, and the dominant wavelength λc is 500nm or more and less than 700nm. In one embodiment, the dominant wavelength λa is preferably less than 400nm, the dominant wavelength λb is preferably 400nm or more and less than 500nm, and the dominant wavelength λc is preferably 500nm or more and less than 700nm.

There is no limitation on the method of adjusting the dominant wavelength. The dominant wavelength may also be adjusted by known methods for adjusting wavelength. The dominant wavelength may also be adjusted using a light source. Examples of the light source include various lasers, light emitting diodes, ultra-high pressure mercury lamps, and metal halide lamps. The dominant wavelength can also be adjusted by a filter. The filter is a member that transmits light of a specific wavelength. Examples of the filter include a filter (Asahi Spectra co., ltd., HMZ 0405).

Conversion Process A

In the conversion step a, the photosensitive resin layer containing the fluorescent material precursor is irradiated with light having a dominant wavelength λb, so that the fluorescent material precursor is converted into a fluorescent material. By converting the fluorescent material precursor into a fluorescent material, invisible information can be given to the photosensitive resin layer.

The mode of the photosensitive resin layer is described in the following item "photosensitive resin layer". Therefore, the photosensitive resin layer in this section will not be described.

The manner in which the dominant wavelength λb is described in the term of "dominant wavelength" described above. The dominant wavelength λb is determined according to the matters described in the above item of "dominant wavelength".

The spectral distribution of the light irradiated to the photosensitive resin layer in the conversion step a may include a wavelength λb1 other than the dominant wavelength λb, as long as the gist of the present invention is not satisfied. When the light irradiated to the photosensitive resin layer in the conversion step a includes the wavelength λb1, the wavelength λb1 is preferably determined within a range satisfying a relationship between λa+.λb1 and λb1 < λc. The wavelength λb1 is preferably determined within a range satisfying a relation of λa < λb1. The wavelength range of light irradiated to the photosensitive resin layer in the conversion step a is preferably 400nm or more and less than 500nm.

Examples of the light source include the light source described in the above item of "dominant wavelength".

The exposure amount upon irradiation of the light of the dominant wavelength λb is preferably 10mJ/cm ² ～1000mJ/cm ² More preferably 50mJ/cm ² ～800mJ/cm ² Particularly preferably 100mJ/cm ² ～500mJ/cm ² 。

The irradiation area of the light can be adjusted, for example, according to the target information. As a method for adjusting the light irradiation region, for example, a method using a photomask having a predetermined light transmitting portion is given. For example, the irradiation region of light can be adjusted by irradiating light through a photomask disposed between the light source and the photosensitive resin layer. Further, by using a light source (for example, laser light) capable of irradiating light having high directivity, the irradiation region of the light can be adjusted.

Observation procedure A

In the observation step a, the region of the photosensitive resin layer exposed to light having a dominant wavelength λb is irradiated with light having a dominant wavelength λc (hereinafter, sometimes referred to as "reference light"), and fluorescence emitted from the fluorescent material is observed.

The manner in which the dominant wavelength λc is described in the term of "dominant wavelength" described above. The dominant wavelength λc is determined according to the matters described in the above item of "dominant wavelength".

The spectral distribution of the light irradiated to the photosensitive resin layer in the observation step a may include a wavelength λc1 other than the dominant wavelength λc, as long as the gist of the present invention is not satisfied. When the light irradiated to the photosensitive resin layer in the observation step a includes the wavelength λc1, the wavelength λc1 is preferably determined within a range satisfying the relationship of λa < λc1 and λb < λc1. The wavelength range of light irradiated to the photosensitive resin layer in the observation step a is preferably 500nm or more and less than 700nm.

Examples of the light source include the light source described in the above item of "dominant wavelength".

The illuminance of the light of the dominant wavelength λc is preferably 1,000lx or more. There is no limitation on the upper limit of the illuminance of the light of the dominant wavelength λc. The upper limit of the illuminance of the light of the dominant wavelength λc can be determined within a range that does not obstruct the observation.

The light irradiation region may include a region of the photosensitive resin layer other than the region exposed to the light having the dominant wavelength λb, as long as the gist of the present invention is not impaired.

In the observation step a, the observer can observe the fluorescence emitted from the fluorescent material with the naked eye. In the observation step a, the observer may observe the fluorescence emitted from the fluorescent material by using an optical device such as a camera, a microscope, or a magnifying glass. However, the main body for observing the fluorescence emitted from the fluorescent material is not limited to a human. If necessary, the fluorescence emitted from the fluorescent material may be observed by a computer, an image pickup device, or the like.

In one embodiment, the observation step a preferably includes observing fluorescence through a filter that blocks the dominant wavelength λc. For example, when the reference light is visible light having a wavelength of 550nm, if the reference light reaches the eye, it may be difficult to observe fluorescence due to the human visual sensitivity (luminosity factor) characteristic. By observing fluorescence through a filter that blocks the dominant wavelength λc, the visibility of fluorescence can be improved. The filter blocking the dominant wavelength ac may be a known filter. Examples of the commercial product of the filter include a long-pass filter (manufactured by FUJIFILM Corporation, SC 62).

Photosensitive resin layer

Hereinafter, the photosensitive resin layer will be described.

[ fluorescent material precursor ]

The photosensitive resin layer contains a fluorescent material precursor. The fluorescent material precursor is converted into a fluorescent material by exposure to light of a dominant wavelength λb. The kind of the fluorescent material precursor is not limited as long as the fluorescent material precursor is a substance having the properties as described above. The fluorescent material precursor may also be a known fluorescent material precursor having the properties as described above.

The fluorescent material precursor is preferably a compound having a triarylmethane structure. Examples of the compound having a triarylmethane structure include pigments having a triarylmethane structure. As the triarylmethane structure, for example, a triphenylmethane structure can be cited.

The fluorescent material precursor is preferably a leuco dye, more preferably a leuco dye having a triarylmethane structure, and even more preferably a leuco dye having a triphenylmethane structure. Examples of the leuco dye include leuco compounds described in the following "dye". The leuco dye is preferably leuco crystal violet.

The photosensitive resin layer may contain 2 or more kinds of fluorescent material precursors.

The content of the fluorescent material precursor in the photosensitive resin layer is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and particularly preferably 0.01 mass% or more, relative to the total mass of the photosensitive resin layer, from the viewpoint of visibility. The content of the fluorescent material precursor in the photosensitive resin layer is preferably 10 mass% or less, more preferably 7 mass% or less, and particularly preferably 5 mass% or less, relative to the total mass of the photosensitive resin layer, from the viewpoint of physical properties of the resin layer after the photosensitive. From the viewpoint of both visibility and physical properties of the resin layer after the light sensing, the content of the fluorescent material precursor in the photosensitive resin layer is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.05 to 3% by mass, relative to the total mass of the photosensitive resin layer.

[ kind ]

The type of the photosensitive resin layer is not limited. The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developer is reduced by exposure (specifically, exposure by light having a dominant wavelength λa) and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to the negative type photosensitive resin layer. The photosensitive resin layer may be a positive type photosensitive resin layer in which the solubility of the exposed portion in a developer is improved by exposure (specifically, exposure by light having a dominant wavelength λa) and the exposed portion is removed by development. The photosensitive resin layer is preferably a photosensitive resin layer that forms a latent image of the resin pattern for forming the wiring.

[ Polymer A ]

The photosensitive resin layer preferably contains a polymer. Hereinafter, the polymer used as a component of the photosensitive resin layer may be referred to as "polymer a". The photosensitive resin layer preferably contains the polymer a, the polymerizable compound, and the polymerization initiator, more preferably contains 10 to 90 mass% of the polymer a, 5 to 70 mass% of the polymerizable compound, and 0.01 to 20 mass% of the polymerization initiator. Hereinafter, the polymer a will be described. The polymerizable compound and the polymerization initiator will be described later.

The polymer a is preferably an alkali-soluble resin.

In terms of improving the resolution by suppressing swelling of the photosensitive resin layer based on the developer, the acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and still more preferably less than 190mgKOH/g. 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. "acid value" is the mass of potassium hydroxide (unit: mg) required for neutralizing 1g of the sample. For example, the acid value can be calculated from the average content of acid groups in the compound. For example, the acid value of the polymer a may be adjusted according to the kind of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.

The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000. By adjusting the weight average molecular weight to 500,000 or less, resolution and developability can be improved. The weight average molecular weight of the polymer a is more preferably 100,000 or less, and still more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, the properties of the developed aggregate and the properties of the unexposed film (for example, edge meltability and chipping property) can be suppressed. The weight average molecular weight of the polymer a is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The term "edge-melting property" refers to the difficulty in projecting the photosensitive resin layer from the end surface of the roll of the photosensitive resin layer wound in a roll shape. The "shavings" means the degree of difficulty in scattering the shavings when the unexposed film is cut by a cutter. For example, if the chips adhere to the upper surface of the photosensitive resin layer, the chips are transferred to the mask in a subsequent exposure step, which causes defective products. 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.

From the viewpoint of suppressing the line width thickening and the deterioration of resolution at the time of focus position shift at the time of exposure, the polymer a preferably contains a structural unit based on a monomer having an aromatic hydrocarbon. Examples of the aromatic hydrocarbon include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit based on the monomer having an aromatic hydrocarbon in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, relative to the total mass of the polymer a. The content of the structural unit based on the monomer having an aromatic hydrocarbon 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. In the case where the photosensitive resin layer contains a plurality of polymers a, the average value of the content of the structural units based on the monomer having an aromatic hydrocarbon is preferably within the above range.

Examples of the monomer having an aromatic hydrocarbon 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, styrene dimer, and styrene trimer). Monomers having aralkyl groups or styrene are preferred. When the monomer component having an aromatic hydrocarbon in the polymer a is styrene, the content of the structural unit based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, still more preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass, based on the total mass of the polymer a.

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

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 (e.g., benzyl (meth) acrylate and chlorobenzyl (meth) acrylate) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). Benzyl (meth) acrylate is preferred. When the monomer component having an aromatic hydrocarbon in the polymer a is benzyl (meth) acrylate, the content of the structural unit based on benzyl (meth) acrylate 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.

The polymer a containing a structural unit based on a monomer having an aromatic hydrocarbon is preferably a polymer obtained by polymerizing a monomer having an aromatic hydrocarbon and at least 1 kind of first monomer and/or at least 1 kind of second monomer.

The polymer a excluding the structural unit based on the monomer having an aromatic hydrocarbon is preferably a polymer obtained by polymerizing at least 1 first monomer, more preferably a polymer obtained by copolymerizing at least 1 first monomer and at least 1 second monomer.

The first monomer is a monomer having a carboxyl group in a 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 acid half ester. (meth) acrylic acid is preferred. The content of the structural unit based on the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass based on the total mass of the polymer a. From the viewpoint of exhibiting good developability and controlling edge meltability, the content of the structural unit based on the first monomer is preferably adjusted to 5 mass% or more. From the viewpoint of high resolution and curl shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, it is preferable to adjust the content of the structural unit based on the first monomer to 50 mass% or less.

The second monomer is a monomer that is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylates. Examples of the (meth) acrylic acid esters 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. Examples of the second monomer include esters of vinyl alcohol. Examples of the esters of vinyl alcohol include vinyl acetate. As the second monomer, for example, (meth) acrylonitrile may be mentioned. Methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is preferred, and methyl (meth) acrylate is more preferred. The content of the structural unit based on the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 17 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 the resolution at the time of the focus position shift at the time of exposure, the polymer a containing a structural unit based on a monomer having an aralkyl group and/or a structural unit based on a monomer having styrene is preferable. For example, copolymers comprising structural units based on methacrylic acid, structural units based on benzyl methacrylate and structural units based on styrene are preferred. For example, copolymers comprising structural units based on methacrylic acid, structural units based on methyl methacrylate, structural units based on benzyl methacrylate and structural units based on styrene are preferred.

The polymer a is preferably a polymer containing 25 to 55 mass% of a structural unit based on a monomer having an aromatic hydrocarbon, 20 to 35 mass% of a structural unit based on a first monomer, and 15 to 45 mass% of a structural unit based on a second monomer. The polymer a is also preferably a polymer containing 70 to 90 mass% of a structural unit based on a monomer having an aromatic hydrocarbon and 10 to 25 mass% of a structural unit based on a first monomer.

The polymer a may have any one of a linear structure, a branched structure, and an alicyclic structure in a side chain. The branched structure and/or alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure in the side chain and/or a monomer containing a group having an alicyclic structure in 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, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

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. Examples of the monomer containing a group having an alicyclic structure in a side chain include (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples of the monomer having an alicyclic structure in the side chain include (meth) acrylic acid (bicyclo [ 2.2.1 ] heptyl-2) ester, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyl adamantyl (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-methylindene (meth) acrylate, 1-indenyl (meth) acrylate, 1-methyl (meth) acrylate, 1-indenyl) acrylate, 1-methyl (meth) acrylate, 1-hydroxy-1-adamantyl (meth) acrylate, 8-hydroxy-methyl (meth) acrylate, 1-hydroxy-adamantyl (meth) acrylate, and (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, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Preference is given to cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecane (meth) acrylate, more preference being given to cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate.

The photosensitive resin layer may contain 1 or 2 or more kinds of polymers a. In the case of using 2 or more kinds of polymers a, it is preferable to use 2 kinds of polymers a containing structural units based on a monomer having an aromatic hydrocarbon, or it is preferable to use a polymer a containing structural units based on a monomer having an aromatic hydrocarbon and a polymer a not containing structural units based on a monomer having an aromatic hydrocarbon. In the latter case, the proportion of the polymer a containing the structural unit based on the monomer having an aromatic hydrocarbon to be used 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 polymer a.

The synthesis of polymer a is preferably carried out by: to a solution obtained by diluting at least 1 of the above monomers with a solvent (for example, acetone, methyl ethyl ketone, and isopropyl alcohol), a radical polymerization initiator (for example, benzoyl peroxide, and azoisobutyronitrile) is added in an appropriate amount, and the mixture is heated and stirred. In some cases, synthesis may be 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 adjust the concentration to a desired level. As the synthesis method, in addition to the solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The glass transition temperature (Tg) of the polymer A is preferably from 30℃to 135 ℃. By using the polymer a having a Tg of 135 ℃ or less, it is possible to suppress the line width thickening and the resolution deterioration at the time of the focus position shift at the time of exposure. The Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, particularly preferably 110℃or lower. In addition, from the viewpoint of improving the edge melting resistance, it is preferable to use the polymer a having Tg of 30 ℃ or higher. The Tg of the polymer A is more preferably 40℃or higher, still more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.

The photosensitive resin layer may contain other resins as the polymer a. Examples of the other resin include acrylic resins, styrene-acrylic copolymers, urethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.

The photosensitive resin layer may contain an alkali-soluble resin as described in the description of the thermoplastic resin layer described later as the polymer a.

The content of the polymer a is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive resin layer. From the viewpoint of controlling the development time, the content of the polymer a is preferably set to 90 mass% or less. From the viewpoint of improving the edge melting resistance, the content of the polymer a is preferably 10 mass% or more.

[ polymerizable Compound ]

The photosensitive resin layer preferably contains a polymerizable compound. In particular, when a negative photosensitive resin layer is used as the photosensitive resin layer, the photosensitive resin layer preferably contains a polymerizable compound. The "polymerizable compound" is a compound which is polymerized by the action of a polymerization initiator described later and is different from the polymer a described above.

The polymerizable compound has a polymerizable group. The type of the polymerizable group is not limited as long as it is a group participating in polymerization. Examples of the polymerizable group include a group having an ethylenically unsaturated group. Examples of the group having an ethylenically unsaturated group include a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group. Examples of the polymerizable group include a group having a cationically polymerizable group. Examples of the group having a cationically polymerizable group include an epoxy group and an oxetanyl group. The polymerizable group is preferably a group having an ethylenically unsaturated group, more preferably an acryl group or a methacryl group.

From the viewpoint of more excellent photosensitivity of the photosensitive resin layer, the polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups in one molecule (i.e., an ethylenically unsaturated compound), more preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (i.e., a polyfunctional ethylenically unsaturated compound). In addition, the number of the ethylenically unsaturated groups in the ethylenically unsaturated compound in one molecule is preferably 6 or less, more preferably 3 or less, and still more preferably 2 or less, from the viewpoint of further excellent resolution and releasability.

From the viewpoint of more excellent balance of photosensitivity and resolution and peelability, the polymerizable compound preferably contains a compound having 2 or 3 ethylenically unsaturated groups in one molecule (i.e., a 2-functional or 3-functional ethylenically unsaturated compound), more preferably contains a compound having 2 ethylenically unsaturated groups in one molecule (i.e., a 2-functional ethylenically unsaturated compound). The content of the 2-functional ethylenically unsaturated compound is preferably 20 mass% or more, more preferably more than 40 mass%, and still more preferably 55 mass% or more, based on the total mass of the polymerizable compound. The content of the 2-functional ethylenically unsaturated compound may be 100 mass% with respect to the total mass of the polymerizable compound. That is, the polymerizable compounds may all be 2-functional ethylenically unsaturated compounds.

Preferable examples of the ethylenically unsaturated compound include (meth) acrylate compounds having a (meth) acryloyl group as a polymerizable group.

The photosensitive resin layer also preferably contains a polymerizable compound having at least 1 aromatic ring and 2 ethylenically unsaturated groups (hereinafter, sometimes referred to as "polymerizable compound B1"). The polymerizable compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule in the polymerizable compound B.

The mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% or more, more preferably 50% or more, further preferably 55% or more, and particularly preferably 60% or more, from the viewpoint of more excellent resolution. The mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, further preferably 90% or less, and particularly preferably 85% or less, from the viewpoint of releasability.

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 condensed rings thereof. Aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The aromatic ring may have a substituent.

The polymerizable compound B1 preferably has a bisphenol structure in view of improving resolution by suppressing swelling of the photosensitive resin layer based on the developer. 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). Bisphenol a structures are preferred.

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. The bisphenol structure may be directly bonded to both ends of 2 polymerizable groups, or may be bonded to each other through 1 or more alkylene oxide groups. As the alkylene oxide group added to both ends of the bisphenol structure, ethylene oxide group or propylene oxide group is preferable, and ethylene oxide group is more preferable. The number of alkylene oxide groups added to the bisphenol structure 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 Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated into the present specification by reference.

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 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi Chemical Co, ltd.) propane, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecyloxypropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxypentadecoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical, manufactured by NK-37co.), and bis (NK-10, manufactured by NK-10, ltd.) phenol.

The polymerizable compound B1 is also preferably a compound represented by the following general formula (B1).

[ chemical formula 1]

In the general formula (B1), 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 N1 and n3 each independently represent an integer of 1 to 39, n1+n3 is an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 is an integer of 0 to 30. The structural units of- (A-O) -and- (B-O) -may be arranged randomly or in blocks. In the structure of- (A-O) -and- (B-O) -in the case where the arrangement of the units is a block, any of the- (A-O) -and- (B-O) -groups may be bisphenol-based. n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. The n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.

The photosensitive resin layer may contain 1 or 2 or more kinds of polymerizable compounds B1.

The content of the polymerizable compound B1 is preferably 10 mass% or more, more preferably 20 mass% or more, based on the total mass of the photosensitive resin layer, from the viewpoint of further excellent resolution. The content of the polymerizable compound B1 is preferably 70 mass% or less, more preferably 60 mass% or less, based on the total mass of the photosensitive resin layer, from the viewpoints of transferability (refer to the property of the photosensitive resin layer when transferred by the photosensitive transfer material) and edge melting (refer to the phenomenon in which the components of the photosensitive resin layer bleed out from the end portions of the photosensitive resin layer).

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

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, urethane 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 Chemical Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shin-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 urethane di (meth) acrylates include propylene oxide modified urethane di (meth) acrylates and ethylene oxide and propylene oxide modified urethane di (meth) acrylates. Examples of commercial products of urethane di (meth) acrylate 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, pentaerythritol (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. "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

In one embodiment, the photosensitive resin layer preferably contains polymerizable compounds B1 and 3 or more functional ethylenically unsaturated compounds, and more preferably contains polymerizable compounds B1 and 2 or more 3 or more functional ethylenically unsaturated compounds. The mass ratio of the total mass of the polymerizable compounds B1 to the 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 still more preferably 1.5:1 to 3:1. In one embodiment, the photosensitive resin layer preferably contains a polymerizable compound B1 and 2 or more 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified products of the ethylenically unsaturated compounds having 3 or more functions include caprolactone-modified (meth) acrylate compounds (for example, KAYARAD (registered trademark) DPCA-20 and Shin Nakamura Chemical co, ltd. A-9300-1 CL), alkylene oxide-modified (meth) acrylate compounds (for example, nippon Kayaku co, ltd. KAYARAD RP-1040, shin Nakamura Chemical co, ltd. ATM-35E and a-9300, and DAICEL-ALLNEX Ltd. EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylates (for example, shin Nakamura Chemical co, ltd. A-GLY-9E), ARONIX (registered trademark) TO-2349 (agosi co, ltd. A-2349), ARONIX-520 (agei co, ltd. A-35E, and TOOTOco. A-510).

The polymerizable compound may be a polymerizable compound having an acid group (for example, a carboxyl group). The acid groups may also form anhydride groups. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) T0-2349 (toagroei co., ltd. Manufactured), ARONIX (registered trademark) M-520 (toagroei co., ltd. Manufactured), and ARONIX (registered trademark) M-510 (toagroei co., ltd. Manufactured). Examples of the polymerizable compound having an acid group include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

The molecular weight (weight average molecular weight in the case where the polymerizable compound has a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.

The photosensitive resin layer may contain 1 or 2 or more kinds of polymerizable compounds.

The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, based on the total mass of the photosensitive resin layer.

[ polymerization initiator ]

The photosensitive resin layer preferably contains a polymerization initiator. In particular, in the case of using a negative photosensitive resin layer as the photosensitive resin layer, the photosensitive resin layer preferably contains a polymerization initiator.

For example, the kind of the polymerization initiator may be selected according to the form of the polymerization reaction. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

The photosensitive resin layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound by receiving activating light such as ultraviolet light, visible light, and X-ray. Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator. Photo radical polymerization initiators are preferred.

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.

The photosensitive resin layer preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof as a photo radical polymerization initiator in terms of photosensitivity, visibility of exposed portions and non-exposed portions, and resolution. 2,4, 5-triarylimidazole dimers and derivatives thereof 2 of the 2,4, 5-triarylimidazole structures 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, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, 4' -bis (diethylamino) benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF corporation), omnirad651 and 369 (trade name: IGM Resins B.V. Co., ltd.), and 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -bisimidazole (Tokyo Chemical Industry Co., ltd.).

Examples of the commercially available photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (o-benzoyloxime) (trade name: IRGACURE (registered trademark) phenyl ] -1-butanone (trade name: omnirad 379EG,IGM Resins B.V, manufactured by BASF)), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (manufactured by Omnirad 379EG,IGM Resins B.V), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: omni 907,IGM Resins B.V, manufactured by Omnirad-1- {4- [4- (2-hydroxy-2-methylpropenyl) phenyl ] -2-oman-one (manufactured by Omni 907,IGM Resins B.V), and 2-hydroxy-1- {4- [ 2-hydroxy-2-propionyl ] -2-phenylpropane } -2-one (manufactured by Omnique) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: manufactured by Omnirad 369,IGM Resins B.V), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: manufactured by Omnirad 1173,IGM Resins B.V), 1-hydroxycyclohexylphenyl ketone (trade name: manufactured by Omnirad 184,IGM Resins B.V), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: manufactured by Omnirad651,IGM Resins B.V), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: manufactured by Omnirad TPO H, manufactured by IGM Resins B.V.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: manufactured by Omnirad 819,IGM Resins B.V), oxime ester-based photopolymerization initiator (trade name: manufactured by Lunar 6,DKSH Holding Ltd), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole (trade name: C4-diphenylimidazole) (manufactured by Omnirad651,IGM Resins B.V), bisphenol-2- (trade name: 3, manufactured by Hantj-phenyl) 4- [ 3, 4, 6-trimethylbenzoyl) phenylpropane (trade name: manufactured by Hantj-3, 4- [ 3, 3-diphenyl ] phenyl ] propane (manufactured by Hantj), 2-dione-2- (o-benzoyloxime) (trade name: TR-PBG-305,Changzhou Tronly New Electronic Materials CO, manufactured by ltd.) 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (o-acetyloxime) (trade name: TR-PBG-326,Changzhou Tronly New Electronic Materials CO, manufactured by ltd.) 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (o-benzoyloxime) (trade name: TR-PBG-391,Changzhou Tronly New F1ectronic Materials CO, manufactured by ltd.).

The photo cation polymerization initiator (photoacid generator) is a compound that receives activating light to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid in response to an activating light having a wavelength of 300nm or more and preferably 300 to 450nm, but the chemical structure thereof is not limited. The photo cation polymerization initiator which does not directly induce the activating 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 inducing the activating light having a wavelength of 300nm or more by being used in combination with the sensitizer.

The photo-cation polymerization initiator is preferably a photo-cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The pKa 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-cation polymerization initiator include onium salt compounds (for example, diaryliodonium salts and triarylsulfonium salts) and quaternary ammonium salts. Examples of the ionic photo-cation polymerization initiator include those described in paragraphs 0114 to 0133 of JP-A2014-085643. Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. Examples of the trichloromethyl s-triazines, diazomethane compounds and imide sulfonate compounds include those described in paragraphs 0083 to 0088 of JP-A2011-221494. Examples of the oxime sulfonate compound include those described in paragraphs 0084 to 0088 of International publication No. 2018/179640.

The photosensitive resin layer preferably contains a photo radical polymerization initiator, more preferably contains at least 1 selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof.

The photosensitive resin layer may contain 1 or 2 or more kinds of polymerization initiators.

The content of the polymerization initiator is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.0 mass% or more, based on the total mass of the photosensitive resin layer. The content of the polymerization initiator is preferably 20 mass% or less, more preferably 15 mass% or less, and still more preferably 10 mass% or less, based on the total mass of the photosensitive resin layer.

Pigment

The photosensitive resin layer preferably contains a dye (hereinafter, also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of color development and having a maximum absorption wavelength changed by an acid, an alkali or a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution. The detailed mechanism is not clear, but the adhesion to an adjacent layer (for example, a water-soluble resin layer) is improved and the resolution is more excellent according to the pigment N.

The phrase "the wavelength is greatly changed by an acid, an alkali or a radical" may refer to any one of a method in which a dye in a developed state is decolorized by an acid, an alkali or a radical, a method in which a dye in a decolorized state is developed by an acid, an alkali or a radical, and a method in which a dye in a developed state is changed to a developed state of another hue. Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. The coloring matter may be a coloring matter which changes the state of color development or decoloration by generating an acid, an alkali or a radical in the photosensitive resin layer by exposure to light and causing an action, or may be a coloring matter which changes the state of color development or decoloration by changing the state (for example, pH) in the photosensitive resin layer by an acid, an alkali or a radical. Further, the coloring matter may be a coloring matter which is not exposed to light but is directly stimulated by an acid, an alkali or a radical to change the state of color development or decoloration.

In terms of visibility and resolution of the exposed portion and the non-exposed portion, the dye N 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. In the case where the photosensitive resin layer is a negative-type photosensitive resin layer, it is preferable that the negative-type photosensitive resin layer contains, as pigments, both a pigment N whose absorption wavelength is greatly changed by radicals and a photo radical polymerization initiator, in terms of visibility and resolution of an exposed portion and a non-exposed portion. In view of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, an alkali, or a radical.

Examples of the coloring mechanism of the coloring matter N include the following: a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator) or a photo alkali generator is added to the photosensitive resin layer, and a radical reactive pigment, an acid reactive pigment or a base reactive pigment (for example, a leuco pigment) develops color by radicals, acids or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator or the photo alkali generator after exposure.

The maximum absorption wavelength of the dye N in the wavelength range of 400nm to 780nm at the time of color development is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion. The dye N may have only 1 maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development, or may have 2 or more. When the dye N 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 pigment N is obtained by: under atmospheric ambient gas, a spectrophotometer was used: UV3100 (manufactured by Shimadzu Corporation), the transmission spectrum of a solution containing pigment N (liquid temperature: 25 ℃ C.) was measured in a range of 400nm to 780nm, and the wavelength at which the intensity of light became extremely small (maximum absorption wavelength) was detected.

Examples of the coloring matter which is developed or decolored by exposure to light include colorless compounds. Examples of the coloring matter to be 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. From the viewpoint of visibility of the exposed portion and the non-exposed portion, a colorless compound is preferable as the coloring matter N.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a colorless compound having a colorless gold amine skeleton (colorless gold amine-based dye). The triarylmethane-based dye or the fluoran-based dye is preferable, and the colorless compound having a triphenylmethane skeleton (triphenylmethane-based dye) or the fluoran-based dye is more preferable.

The colorless compound is preferably a lactone ring, a sultone ring (sultone ring), or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion. The lactone ring, sultone ring or sultone ring in the colorless compound can be reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator to thereby change the colorless compound to a closed-loop state to decolorize or to change the colorless compound to an open-loop state to develop color. As the colorless compound, a compound having a lactone ring, a sultone ring, or a sultone ring and opening the lactone ring by a radical or an acid and developing a color is preferable, and a compound having a lactone ring and opening the lactone ring by a radical or an acid and developing a color is more preferable.

Examples of the dye N include the following dyes and colorless compounds. Specific examples of the dye contained in the dye N include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsine (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metamine yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol (xylenol) blue, methyl orange, para-methyl red, congo red, benzored violet (benzopurline) 4B, alpha-naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), paragrade red (parafuchsin), victoria pure blue (victoria pure blue) -naphthalene sulfonate, victoria pure blue (Hodogaya Chemical, co.) ltd), oil blue #603 (Orient Chemical Industries co., ltd), oil powder #312 (Orient Chemical Industries co., ltd), oil red 5B (Orient Chemical Industries co., ltd), oil scarlet #308 (Orient Chemical Industries co., ltd), oil red OG (Oriont Chemical Industries co., ltd), oil red RR (Orient Chemical Industries co., ltd), oil green #502 (Orient Chemical Industries co., ltd), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl imino naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyl imino naphthoquinone, gold amine, 4-p-diethylaminophenyl imino naphthoquinone 2-carboxystearyl amino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the colorless compound contained in the dye N 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-toluidine) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamin) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylanilino fluoran, 3- (N, N-diethylamino) -6-methyl-6- (N-ethyl-p-toluidine), 3, 6-dimethoxyfluoran, 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-anilino fluoran, and 4-dimethylamino-fluoran 3- (N, 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-dimethylanilinofluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-ethyl-2-methylindol-3-yl) phthalide, 3- (1-ethyl-2-methylindol-3-yl) phthalide, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose wavelength is greatly changed by radical absorption, and more preferably a dye whose color is developed by radical, in terms of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. As pigment N, preference is given to leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate.

The photosensitive resin layer may contain 1 or 2 or more pigments N.

The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the photosensitive resin layer, in terms of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution.

The content of the dye N is the content of the dye when all the dye N contained in the photosensitive resin layer is in a color development state. Hereinafter, a method for determining the content of the dye N will be described by taking a dye that develops color by a radical as an example. A solution in which 0.001g of a dye was dissolved in 100mL of methyl ethyl ketone and a solution in which 0.01g of a dye was dissolved in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, irgacure OXE01 (trade name, BASF Japan ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, thereby generating radicals and bringing all the pigments into a color development state. The absorbance of each solution having a liquid temperature of 25℃was measured under atmospheric air using a spectrophotometer (manufactured by UV3100, shimadzu Corporation), and a calibration curve was prepared. Next, absorbance of the solution in which all the pigments were developed was measured in the same manner as described above except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive resin layer was calculated based on the calibration curve from the absorbance of the obtained solution containing the photosensitive resin layer.

[ thermally crosslinkable Compound ]

In the case where the photosensitive resin layer is a negative type photosensitive resin layer, the photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present invention, the thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound but is treated as a thermally crosslinkable compound.

Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. The blocked isocyanate compound is preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, when the polymer a and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the formed film decreases, and the function when the film obtained by curing the negative photosensitive resin layer is used as a protective film tends to be enhanced. The blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is preferably 100℃to 160℃and more preferably 130℃to 150 ℃. The dissociation temperature of the blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured using a differential scanning calorimeter and analyzed by DSC (Differential scanning caiorimetry: differential scanning calorimeter)". As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited to the above-described differential scanning calorimeter.

Examples of the blocking agent having a dissociation temperature of 100 to 160℃include active methylene compounds (e.g., malonic acid diesters (e.g., dimethyl malonate, diethyl malonate, di-N-butyl malonate, and di-2-ethylhexyl malonate)), oxime compounds (e.g., aldoxime, acetoxime, methylethyl ketoxime, and cyclohexanone oxime) and the like having a structure represented by-C (=N-OH) -in the molecule. From the viewpoint of storage stability, the blocking agent having a dissociation temperature of 100 to 160℃is preferably at least 1 selected from oxime compounds, for example.

For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving brittleness of the film, improving adhesion to a transfer object, and the like. The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanating hexamethylene diisocyanate to protect it. Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferable in that the dissociation temperature is set to a preferable range more easily than a compound having no oxime structure and development residues are easily reduced.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group may be a known polymerizable group. The polymerizable group is preferably a radical polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated group (for example, (meth) acryloyloxy group, (meth) acrylamide group and styryl group) and a group having an epoxy group (for example, glycidyl group). The polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and further preferably an acryloyloxy group.

Examples of the commercial products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, etc. (the above is made by SHOWA DENKO K.K.), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, etc., made by Asahi Kasei Chemicals Corporation).

As the blocked isocyanate compound, a compound having the following structure can be used.

[ chemical formula 2]

The photosensitive resin layer may contain 1 or 2 or more thermally crosslinkable compounds.

The content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive resin layer.

[ additive ]

The photosensitive resin layer may contain known additives as required. Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound (e.g., triazole), a benzotriazole, a carboxybenzotriazole, a pyridine (e.g., isonicotinamide), a purine base (e.g., adenine), and a surfactant. The additives may be used singly or in an amount of 1 kind or 2 or more kinds.

The photosensitive resin 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. Phenothiazine, phenoxazine or 4-methoxyphenol are preferred. Examples of the radical polymerization inhibitor include naphthylamine group, cuprous chloride, nitrosophenyl hydroxylamine aluminum salt and diphenyl nitrosoamine. In order not to impair the sensitivity of the photosensitive resin layer, nitrosophenyl hydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.

Examples of benzotriazoles 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 carboxybenzotriazoles 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. As the carboxybenzotriazoles, for example, commercially available products such as CBT-1 (JOHOKU CHEMICAL co., ltd., trade name) can be used.

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass% based on the total mass of the photosensitive resin layer. When the content is 0.01 mass% or more, the storage stability of the photosensitive resin layer is more excellent. On the other hand, when the content is 3 mass% or less, the maintenance of sensitivity and the suppression of discoloration of the dye are more excellent.

The photosensitive resin layer may contain a sensitizer. Examples of the sensitizer include known sensitizers, dyes and pigments. 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 (e.g., 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.

The photosensitive resin layer may contain 1 or 2 or more sensitizers.

The content of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the photosensitive resin layer, from the viewpoints of improving the sensitivity to a light source and improving the curing speed based on the balance of the polymerization speed and chain transfer.

The photosensitive resin layer may contain at least 1 selected from 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 photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include surfactants described in paragraphs 0060 to 0071 of JP-A-4502784, paragraph 0017 and JP-A-2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable. Examples of the commercial products of the fluorine-based surfactant include MEGAFAC (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, manufactured by Sumitomo 3M 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, manufactured by AGC Inc.), polyFox (e.g., PF636, PF656, PF6320, PF6520 and PF7002, manufactured by OMNOVA Solutions Inc.) and FTERGENT (710 FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC and 681 manufactured by Neos Inc.).

As the fluorine-based surfactant, an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and a functional group portion containing a fluorine atom is cleaved when heat is applied, so that the fluorine atom volatilizes can be preferably used. Examples of the fluorine-based surfactant include MEGAFAC DS series (chemical industry journal of date (2016, 2, 22 days) and daily industrial news (2016, 2, 23 days) manufactured by DIC Corporation, for example MEGAFAC DS-21).

As the fluorine-based surfactant, a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group is also preferably used.

As the fluorine-based surfactant, a block polymer can also be used.

As the fluorine-based surfactant, a fluorine-containing polymer compound including a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) can be preferably used.

As the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. For example, MEGAFAC (for example, RS-101, RS-102, RS-718K, RS-72-K, DIC CORPORATION) can be mentioned.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC (for example, L10, L31, L61, L62, 10R5, 17R2 and 25R2, manufactured by BASF corporation), TETRONIC (for example, 304, 701, 704, 901, 904 and 150R1, manufactured by BASF corporation), SOLSPERSE 20000 (manufactured by The Lubrinzol corporation), NCW-101 (manufactured by FUJIFILM Wako Pure Chemical Corporation), NCW-1001 (manufactured by FUJIFILM Wako Pure Chemical Corporation), NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (for example, D-6112-W and D-6315, tamo & Fakey Co., ltd, ltdCo., manufactured by Chemical Co., ltd. 1010, manufactured by Chemical Co., ltd. And Chemical Co., ltd. No. 400, and YNSYN.400.

As the fluorine-based surfactant, for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used. However, from the viewpoint of improving environmental suitability, as the fluorine-based surfactant, a substitute material of perfluorooctanoic acid (PFOA) or perfluorooctane sulfonate (PFOS) is preferably used.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminal ends.

Examples of the surfactant include DOWSIL8032 ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH30PA, and Toray Silicone SH8400 (from Dow Corning Toray Co., ltd.). Examples of the surfactant include X-22-4952, X-22-4272, X-22-6266, KF-351A, K354-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (manufactured by Shin-Etsu Chemical Co., ltd.). Examples of the surfactant include F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive performance Materials Inc. above). Examples of the surfactant include BYK307, BYK323, and BYK330 (BYK co., LTD).

The photosensitive resin layer may contain known additives such as metal oxide particles, antioxidants, dispersants, acid-proliferation agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic anti-settling agents, and inorganic anti-settling agents.

The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-085643, the contents of which are incorporated herein by reference.

[ impurity ]

The photosensitive resin layer may contain a predetermined amount of impurities. Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. The halide ion, sodium ion and potassium ion are preferably contained in the following amounts because they are easily mixed with impurities.

The content of impurities in the photosensitive resin layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less on a mass basis. The content of impurities may be 1ppb or more or 0.1ppm or more on a mass basis. As a method for setting the impurity content to the above range, a method for selecting a raw material having a small impurity content as a raw material, and preventing the mixing of impurities, cleaning and removing the impurities at the time of producing a photosensitive resin layer can be exemplified. In this way, the impurity amount can be set within the above range. The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

The photosensitive resin layer preferably contains a small amount of a compound such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, hexane, and the like. The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100ppm or less, more preferably 20ppm or less, and even more preferably 4ppm or less on a mass basis. The content of the compound may be 10ppb or more or 100ppb or more in terms of mass relative to the total mass of the photosensitive resin layer. The content of these compounds can be suppressed by the same method as the method for adjusting the content of the impurities of the metal described above. The content of the compound can be quantified by a known measurement method.

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

[ pigment ]

The photosensitive resin layer may be a colored resin layer containing a pigment. In recent years, in order to protect a liquid crystal display window, a cover glass (cover glass) in which a black frame-like light shielding layer is formed on a rear surface peripheral edge portion of a transparent glass substrate or the like is sometimes mounted on the liquid crystal display window included in an electronic device. In order to form such a light shielding layer, a colored resin layer may be used. The pigment may be appropriately selected according to a desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white. In the case of forming a black-based pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (for example, an organic pigment or an inorganic pigment) can be appropriately selected as long as the effect of the present invention is not impaired. From the viewpoint of optical density, examples of the preferable black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, and graphite, and carbon black is particularly preferable. As the carbon black, carbon black having at least a part of the surface coated with a resin is preferable from the viewpoint of surface resistance.

The number average particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm, from the viewpoint of dispersion stability. The "particle diameter" is the diameter of a circle when the area of the pigment particle is obtained from a photographic image of the pigment particle taken by an electron microscope and the same area as the area of the pigment particle is considered. The number average particle diameter is an average value obtained by obtaining the above particle diameter for any 100 particles and averaging the obtained 100 particle diameters.

As the white pigment, the white pigments described in paragraphs 0015 and 0114 of jp 2005-007765 a can be used. Specifically, the inorganic pigment contained in the white pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide, and still more preferably titanium oxide. The inorganic pigment is preferably rutile-type or anatase-type titanium oxide, and more preferably rutile-type titanium oxide.

The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more kinds of treatments. Thus, the catalytic activity of titanium oxide is suppressed, and the heat resistance and the gloss reducing property are improved. In terms of reducing the thickness of the heated photosensitive resin layer, at least one of an alumina treatment and a zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both of the alumina treatment and the zirconia treatment are more preferable.

In the case where the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of further excellent dispersibility. As the Color pigment, for example, examples thereof include Victoria pure blue BO (Color Index) (hereinafter, C.I.) 42595, gold amine (C.I. 41000), fat black (fat black) HB (C.I. 26150), monolite yellow (yellow) GT (C.I. pigment yellow 12), permanent yellow (yellow) GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent carmine (permanent carmine) FBB (C.I. pigment Red 146), hestapam red (Hostapam red) ESB (C.I. pigment Red 19), permanent ruby red (permanent ruby) H (C.I. pigment Red 11), fastel powder (yellow) B sepera (C.I. pigment Red 81), permanent yellow (yellow) GR (C.I. pigment Red 84), permanent yellow HR (C.I. pigment Red 83), permanent carmine (C.I. pigment Red 15), hei. pigment Red (C.I. pigment Red 149), hemsley (C.I. pigment Red 215), permanent red (permanent ruby) FBH (C.I. pigment Red 11), fastel powder (yellow) pigment Red (yellow 81), permanent yellow (C.I. pigment Red 35), permanent red (C.I. pigment Red 35, C.I. pigment Red (C.I. pigment Red 15), permanent red (C.I. pigment red) pigment red (C.I. pigment red) yellow (C.15), and pigment yellow (C.I.I. pigment red (yellow) pigment red (yellow) 3). 1. C.i. pigment-blue 15: 4. c.i. pigment blue 22, c.i. pigment blue 60, c.i. pigment blue 64, and c.i. pigment violet 23. C.i. pigment red 177 is preferred.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, still more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, relative to the total mass of the photosensitive resin layer.

When the photosensitive resin layer contains a pigment other than the black pigment (white pigment and color pigment), the content of the pigment other than the black pigment is preferably 30 mass% or less, more preferably 1 mass% to 20 mass%, and still more preferably 3 mass% to 15 mass% relative to the total mass of the black pigment.

When the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed of a photosensitive resin composition, the black pigment (preferably, carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion may be prepared by: the mixture obtained by mixing the black pigment and the pigment dispersant in advance is added to an organic solvent (or carrier) and dispersed by a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle means a medium portion for dispersing the pigment when the pigment dispersion is prepared, and is a liquid state and includes a binder component for maintaining the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.

Examples of the dispersing machine include a kneader, a roll mill, a grinding mill, a super mill (super mill), a dissolver, a homomixer, and a sand mill. The mixture may also be subjected to micronization by mechanical grinding, using friction. For the disperser and the fine pulverization, a description of "pigment dictionary" (manufactured by kubang, first edition, kuku shop, 2000, page 438, page 310) can be referred to.

[ thickness ]

In general, the thickness of the photosensitive resin layer is 0.1 μm to 300. Mu.m, preferably 0.2 μm to 100. Mu.m, more preferably 0.5 μm to 50. Mu.m, still more preferably 0.5 μm to 15. Mu.m, particularly preferably 0.5 μm to 10. Mu.m, and most preferably 0.5 μm to 8. Mu.m. Thus, the developability of the photosensitive resin layer is improved, and the resolution is improved. The thickness of the photosensitive resin layer is preferably 0.5 μm to 5 μm, more preferably 0.5 μm to 4 μm, and even more preferably 0.5 μm to 3 μm. The thickness of the photosensitive resin layer was calculated as an average value of the thicknesses of 5 portions measured by cross-sectional observation.

[ transmittance ]

The transmittance of the photosensitive resin layer for light having a wavelength of 365nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more, from the viewpoint of further excellent adhesion. The transmittance of the light is preferably 99.9% or less.

[ method of Forming photosensitive resin layer ]

The method for forming the photosensitive resin layer is not limited. The photosensitive resin layer is formed, for example, by applying a photosensitive resin composition and drying if necessary. The photosensitive resin composition preferably contains various components and solvents for forming the photosensitive resin layer. The preferable range of the content ratio of each component to the total solid content of the photosensitive resin composition is the same as the preferable range of the content ratio of each component to the total mass of the photosensitive resin 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 (e.g., N-propyl acetate), amide solvents, lactone solvents, and mixed solvents containing 2 or more of these solvents.

The solvent preferably contains at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, the solvent mixture contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from the group consisting of a ketone solvent and a cyclic ether solvent, and still more preferably contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and 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 (for example, propylene glycol monomethyl ether acetate), 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 solvent described in paragraph 0014 of japanese patent application laid-open publication No. 2018-177889, which are incorporated herein by reference, may be used.

The photosensitive resin composition may contain 1 or 2 or more solvents.

The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition.

Examples of the method for coating the photosensitive resin composition include a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (i.e., a slit coating method).

As a method for drying the coating film of the photosensitive resin composition, preferably, the drying is performed by heating or drying under reduced pressure. The drying temperature is preferably 80℃or higher, more preferably 90℃or higher. The drying temperature is preferably 130 c or less, more preferably 120℃or lower. Can also be changed continuously drying is performed at a temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The drying time is preferably 600 seconds or less, more preferably 300 seconds or less.

[ laminate ]

In one embodiment, the photosensitive resin layer may be a part of the laminate. That is, in the information providing method according to one embodiment, the photosensitive resin layer included in the laminate may be irradiated with specific light (for example, light having the dominant wavelength λb and light having the dominant wavelength λc).

Examples of the layers other than the photosensitive resin layer in the laminate include a substrate, a conductive layer, a thermoplastic resin layer, an intermediate layer, and a refractive index adjusting layer.

A specific example of the layer structure of the laminate is shown below. However, the layer structure of the laminate is not limited to the following specific examples.

(1) Substrate/photosensitive resin layer

(2) Substrate/photosensitive resin layer/thermoplastic resin layer

(3) Substrate/photosensitive resin layer/intermediate layer/thermoplastic resin layer

(4) Substrate/conductive layer/photosensitive resin layer

(5) Substrate/conductive layer/photosensitive resin layer/thermoplastic resin layer

(6) Substrate/conductive layer/photosensitive resin layer/intermediate layer/thermoplastic resin layer

(substrate)

The laminate may also comprise a substrate. The laminate preferably includes a base material and a photosensitive resin layer in this order.

The kind of the base material is not limited. Examples of the base material include a resin substrate, a glass substrate, and a semiconductor substrate. The resin substrate preferably includes at least 1 selected from cycloolefin polymers and polyimides. The thickness of the resin substrate is preferably 5 μm to 200. Mu.m, more preferably 10 μm to 100. Mu.m. The thickness of the resin substrate was calculated as an average value of thicknesses of 5 portions measured by cross-sectional observation.

A preferred embodiment of the substrate is described in, for example, paragraph 0140 of international publication No. 2018/155193. The contents of the above publications are incorporated into the present specification by reference.

(conductive layer)

The laminate may also include a conductive layer. The laminate preferably includes a conductive layer and a photosensitive resin layer in this order, and more preferably includes a base material, a conductive layer, and a photosensitive resin layer in this order. That is, the conductive layer is preferably disposed between the substrate and the photosensitive resin layer.

The laminate may contain 2 or more conductive layers. In the case where the laminate includes 2 or more conductive layers, the conductive layers may be disposed on both surfaces of the substrate. When the laminate includes 2 or more conductive layers, 2 or more conductive layers may be stacked on one surface of the base material. When the laminate includes 2 or more conductive layers, the material of at least 2 conductive layers is preferably different from each other.

Examples of the component of the conductive layer include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese. Examples of the component of the conductive layer include ITO (indium tin oxide) and IZO (indium zinc oxide). Examples of the component of the conductive layer include metal nanoparticles and metal nanowires.

The conductive layer is preferably at least 1 selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer in view of conductivity and fine line formation.

A preferred embodiment of the conductive layer is described in, for example, paragraph 0141 of international publication No. 2018/155193. The contents of the above publications are incorporated into the present specification by reference.

(thermoplastic resin layer)

The laminate may also include a thermoplastic resin layer. The laminate preferably includes a base material, a photosensitive resin layer, and a thermoplastic resin layer in this order.

The thermoplastic resin layer contains a resin. At least a portion or all of the resin is a thermoplastic resin. The resin in the thermoplastic resin layer is preferably a thermoplastic resin.

The thermoplastic resin is preferably an alkali-soluble resin. Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

From the viewpoints of developability and adhesion of the thermoplastic resin layer to the adjacent layer, an acrylic resin is preferable as the alkali-soluble resin. The "acrylic resin" refers to a resin having at least 1 selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. In the acrylic resin, the total content of the structural units derived from (meth) acrylic acid, the structural units derived from (meth) acrylic acid ester, and the structural units derived from (meth) acrylic acid amide is preferably 50 mass% or more relative to the total mass of the acrylic resin. The total content of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

The alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, more preferably an acrylic resin containing a carboxyl group having an acid value of 60mgKOH/g or more. The acid value is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, still more preferably 200mgKOH/g or less, particularly preferably 150mgKOH/g or less.

Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include alkali-soluble resins, which are carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more, among the polymers described in paragraph 0025 of JP-A2011-095716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of JP-A2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A2016-224162. The copolymerization ratio of the carboxyl group-containing structural units in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoints of developability and adhesion of the thermoplastic resin layer to an adjacent layer.

The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxyl group and a carboxyl group), and a polyaddition reactive group (e.g., an epoxy group and a (blocked) isocyanate group).

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 1 to 10 tens of thousands, and still more preferably 2 to 5 tens of thousands.

The thermoplastic resin layer may contain 1 or 2 or more alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoints of developability and adhesion of the thermoplastic resin layer to the adjacent layer.

The thermoplastic resin layer preferably contains a dye (hereinafter, sometimes referred to as "dye B") whose maximum absorption wavelength at the wavelength range of 400nm to 780nm at the time of color development is 450nm or more, and whose maximum absorption wavelength is changed by an acid, an alkali or a radical. The preferred embodiment of the dye B is the same as that of the dye N described above, except for the point described below.

In terms of visibility and resolution of the exposed portion and the non-exposed portion, the dye B 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 an acid. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains both a dye whose wavelength is greatly changed by an acid as a dye B and a compound which generates an acid by light, which will be described later.

The thermoplastic resin layer may contain 1 or 2 or more pigments B.

The content of the dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed portion and the non-exposed portion. The content of the dye B is the content of the dye when all the dye B contained in the thermoplastic resin layer is in a color development state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by a radical as an example. A solution in which 0.001g of a dye was dissolved in 100mL of methyl ethyl ketone and a solution in which 0.01g of a dye was dissolved in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, irgacure OXE01 (trade name, BASF Japan ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, thereby generating radicals and bringing all the pigments into a color development state. The absorbance of each solution having a liquid temperature of 25℃was measured under atmospheric air using a spectrophotometer (manufactured by UV3100, shimadzu Corporation), and a calibration curve was prepared. Next, absorbance of the solution in which the pigment was developed entirely was measured in the same manner as described above except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The amount of the pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer and based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, sometimes referred to as "compound C").

The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an activating light such as ultraviolet rays or visible rays. As the compound C, a known photoacid generator, photobase generator, and photo radical polymerization initiator (photo radical generator) can be used.

From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator. The photo-acid generator may be a photo-cation polymerization initiator which the photosensitive resin layer may contain, and the same is preferable except for the point described below.

The photoacid generator preferably contains at least 1 selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion. The photoacid generator preferably has the following structure.

[ chemical formula 3]

The thermoplastic resin layer may also contain a photo radical polymerization initiator. The photo radical polymerization initiator may be included in the photosensitive resin layer, and the same preferable mode is also adopted.

The thermoplastic resin composition may also contain a photobase generator. Examples of the photobase generator include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, o-carbamoyl hydroxyamide, o-carbamoyl oxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane 1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaminocobalt (III) tris (triphenylmethyl borate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine, and 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.

The thermoplastic resin layer may contain 1 or 2 or more kinds of compound C.

From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the resolution of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% with respect to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer preferably contains a plasticizer in terms of resolution, adhesion of the thermoplastic resin layer to an adjacent layer, and developability.

The molecular weight of the plasticizer (weight average molecular weight in the case where the plasticizer has a molecular weight distribution) is preferably smaller than that of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that exhibits plasticity by being compatible with the alkali-soluble resin, and from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in a molecule, and more preferably a polyalkylene glycol compound. The alkylene oxide group contained in the plasticizer more preferably has a polyethylene oxide structure or a polypropylene oxide structure.

The plasticizer preferably contains a (meth) acrylate compound from the viewpoints of resolution and storage stability. From the viewpoints of compatibility, resolution, and adhesion of the thermoplastic resin layer to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound. The (meth) acrylate compound used as the plasticizer includes (meth) acrylate compounds described as polymerizable compounds contained in the photosensitive resin layer. In the laminate, when the thermoplastic resin layer is laminated in direct contact with the negative photosensitive resin layer, it is preferable that the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth) acrylate compound. By containing the same (meth) acrylate compound in each of the thermoplastic resin layer and the negative photosensitive resin layer, the diffusion of components between layers is suppressed and the storage stability is improved.

In the case where the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer.

The (meth) acrylate compound used as the plasticizer is preferably a multifunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule, from the viewpoints of resolution of the thermoplastic resin layer, adhesion of the thermoplastic resin layer to an adjacent layer, and developability.

As the (meth) acrylate compound used as the plasticizer, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.

The thermoplastic resin layer may contain 1 or 2 or more plasticizers.

The content of the plasticizer is preferably 1 to 70 mass%, more preferably 10 to 60 mass%, and even more preferably 20 to 50 mass% with respect to the total mass of the thermoplastic resin layer, from the viewpoints of resolution of the thermoplastic resin layer, adhesion between the thermoplastic resin layer and the adjacent layer, and developability.

The thermoplastic resin layer may also contain a sensitizer. Examples of the sensitizer include those that the photosensitive resin layer may contain.

The thermoplastic resin layer may contain 1 or 2 or more sensitizers.

The content of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion.

The thermoplastic resin layer may contain a known additive such as a surfactant, if necessary, in addition to the above components. Examples of the surfactant include the surfactants described in the above item of "photosensitive resin layer".

The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese patent application laid-open No. 2014-085643, the disclosure of which is incorporated herein by reference.

The thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion of the thermoplastic resin layer to the adjacent layer. The thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less from the viewpoints of developability and resolution. The thickness of the thermoplastic resin layer was calculated as an average value of the thicknesses of 5 portions measured by cross-sectional observation.

The thermoplastic resin layer is formed, for example, by applying a thermoplastic resin layer-forming composition and drying if necessary.

The thermoplastic resin layer-forming composition preferably contains various components and solvents for forming the thermoplastic resin layer. The preferable range of the content ratio of each component to the total solid content of the thermoplastic resin layer-forming composition is the same as the preferable range of the content ratio of each component to the total mass of the thermoplastic resin layer.

Examples of the solvent include the solvents described in the above item of "photosensitive resin layer".

The thermoplastic resin layer-forming composition may contain 1 or 2 or more solvents.

The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the thermoplastic resin layer-forming composition.

Examples of the coating method of the thermoplastic resin layer include known coating methods (for example, slit coating, spin coating, curtain coating, and inkjet coating).

(intermediate layer)

The laminate may include an intermediate layer between the photosensitive resin layer and the thermoplastic resin layer. The intermediate layer disposed between the photosensitive resin layer and the thermoplastic resin layer can suppress mixing of the components of the photosensitive resin layer and the thermoplastic resin layer.

The intermediate layer may also contain the already described phosphor precursors.

As the intermediate layer, for example, a water-soluble resin layer containing a water-soluble resin is given. Further, as the intermediate layer, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese patent application laid-open No. 5-072724 can be mentioned. If the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved and the time load of the exposure machine is reduced, thereby improving productivity. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above-mentioned publications and the like. The oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1% by mass aqueous solution of sodium carbonate at 22 ℃) is preferable.

The water-soluble resin layer contains a resin. Part or all of the resin is a water-soluble resin. Examples of the water-soluble resin include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins. The water-soluble resin may be, for example, a copolymer of (meth) acrylic acid and a vinyl compound. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) acrylic acid allyl ester is preferable, and a copolymer of methacrylic acid/methacrylic acid allyl ester is more preferable. When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio (mol%) is, for example, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and still more preferably 10,000 or more. The weight average molecular weight of the water-soluble resin is preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less. The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

In order to further improve the interlayer mixing suppression capability of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a resin different from the resin contained in the layer disposed on one side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other side. For example, when the photosensitive resin layer contains the polymer a and the thermoplastic resin layer contains the thermoplastic resin (alkali-soluble resin), the resin of the water-soluble resin layer (intermediate layer) is preferably a resin different from the polymer a and the thermoplastic resin (alkali-soluble resin).

From the viewpoint of further improving the oxygen barrier property and interlayer mixing inhibition ability, the water-soluble resin preferably contains polyvinyl alcohol, more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

The water-soluble resin layer may contain 1 or 2 or more water-soluble resins.

The content of the water-soluble resin is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more, based on the total mass of the water-soluble resin layer (intermediate layer), from the viewpoint of further improving the oxygen barrier property and interlayer mixing inhibition ability. The content of the water-soluble resin is, for example, preferably 99.9 mass% or less, and more preferably 99.8 mass% or less, based on the total mass of the water-soluble resin layer (intermediate layer).

The intermediate layer may contain a known additive such as a surfactant, if necessary. Examples of the surfactant include the surfactants described in the above item of "photosensitive resin layer".

The thickness of the intermediate layer is preferably 0.1 μm to 5. Mu.m, more preferably 0.5 μm to 3. Mu.m. When the thickness of the intermediate layer is within the above range, the interlayer mixing suppression ability is excellent without decreasing the oxygen barrier property. Further, an increase in the removal time of the intermediate layer during development can also be suppressed. The thickness of the intermediate layer was calculated as an average value of the thicknesses of 5 portions measured by cross-sectional observation.

The intermediate layer is formed, for example, by applying an intermediate layer-forming composition and drying if necessary.

The intermediate layer-forming composition preferably contains various components and solvents for forming the intermediate layer. The preferable range of the content ratio of each component to the total solid content of the composition for forming an intermediate layer is the same as the preferable range of the content ratio of each component to the total mass of the intermediate layer.

The solvent is preferably at least 1 selected from water and water-miscible organic solvents (Water Miscibility), and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

The intermediate layer-forming composition may contain 1 or 2 or more solvents.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the intermediate layer-forming composition.

Examples of the method for applying the intermediate layer-forming composition include known application methods (for example, slit coating, spin coating, curtain coating, and inkjet coating).

(refractive index adjusting layer)

The laminate may include a refractive index adjustment layer. The refractive index adjusting layer may be a known refractive index adjusting layer. Examples of the material contained in the refractive index adjustment layer include polymers, polymerizable compounds, metal salts, and particles.

Examples of the method for controlling the refractive index of the refractive index adjusting layer include a method using a polymer having a predetermined refractive index alone, a method using a polymer and particles, and a method using a composite of a metal salt and a resin.

Examples of the polymer and the polymerizable compound include the polymer a and the polymerizable compound described in the item of the "photosensitive resin layer".

Examples of the particles include metal oxide particles and metal particles. The metal in the metal oxide particles includes a half metal such as B, si, ge, as, sb and Te.

The average primary particle diameter of the particles is preferably 1nm to 200nm, more preferably 3nm to 80nm, from the viewpoint of transparency of the cured film. The average primary particle diameter of the particles was calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the shape of the particles is not spherical, the longest side is set to have a particle diameter.

The metal oxide particles are preferably selected from zirconia particles (ZrO ₂ Particles, nb ₂ O ₅ Particles, titanium oxide particles (TiO ₂ Particles), silica particles (SiO ₂ Particles) and their composite particles. From the viewpoint of easy adjustment of refractive index, the metal oxide particles are more preferably at least 1 selected from the group consisting of zirconia particles and titania particles.

Examples of the commercial products of the metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F76), zirconia particles (manufactured by NanoUse OZ-S30M, nissan Chemical Industries, ltd.) and zirconia particles (manufactured by NanoUse OZ-S30K, nissan Chemical Industries, ltd.).

The refractive index adjustment layer may contain 1 or 2 or more kinds of particles.

The content of the particles in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, based on the total mass of the refractive index adjustment layer. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer.

The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive resin layer. The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The refractive index of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

The thickness of the refractive index adjusting layer is preferably 50nm to 500nm, more preferably 55nm to 110nm, and still more preferably 60nm to 100nm. The thickness of the refractive index adjustment layer was calculated as an average value of arbitrary 5 points measured by cross-sectional observation based on a Scanning Electron Microscope (SEM).

The refractive index adjusting layer is formed, for example, by applying a composition for forming a refractive index adjusting layer and drying if necessary.

The composition for forming a refractive index adjustment layer preferably contains various components and solvents for forming the refractive index adjustment layer. The preferable range of the content ratio of each component to the total solid content of the composition for forming a refractive index adjustment layer is the same as the preferable range of the content ratio of each component to the total mass of the refractive index adjustment layer.

The solvent is preferably at least 1 selected from water and water-miscible organic solvents (Water Miscibility), and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

The composition for forming a refractive index adjusting layer may contain 1 or 2 or more solvents.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition for forming the refractive index adjustment layer.

Examples of the method for applying the composition for forming the refractive index adjusting layer include known application methods (for example, slit coating, spin coating, curtain coating, and inkjet coating).

(method for producing laminate)

The method for producing the laminate is not limited. The laminate may be formed by using the above-described method for forming each layer. The laminate may be formed using a photosensitive transfer material including a photosensitive resin layer. That is, the photosensitive resin layer may be a photosensitive resin layer derived from a photosensitive transfer material. For example, the laminate is formed by transferring at least a part of a layer included in the photosensitive transfer material onto an arbitrary member (for example, a base material). For example, a laminate including a substrate, a photosensitive resin layer, and a temporary support is formed by bonding a photosensitive transfer material including the temporary support and the photosensitive resin layer to the substrate.

The layer structure of the laminate formed using the photosensitive transfer material may be the same as that of the laminate described above. The laminate formed using the photosensitive transfer material may include a temporary support. The temporary support is a member derived from a photosensitive transfer material. A specific example of the layer structure of the laminate including the temporary support is shown below. However, the layer structure of the laminate including the temporary support is not limited to the following specific examples. The temporary support in the laminate may be removed as needed.

(1) Substrate/photosensitive resin layer/temporary support

(2) Substrate/photosensitive resin layer/thermoplastic resin layer/temporary support

(3) Substrate/photosensitive resin layer/intermediate layer/thermoplastic resin layer/temporary support

(4) Substrate/conductive layer/photosensitive resin layer/temporary support

(5) Substrate/conductive layer/photosensitive resin layer/thermoplastic resin layer/temporary support

(6) Substrate/conductive layer/photosensitive resin layer/intermediate layer/thermoplastic resin layer/temporary support

Bonding of the photosensitive transfer material to an arbitrary member (for example, a base material) is preferably performed under pressure and heat. For bonding the photosensitive transfer material to any member, for example, a known laminator such as a vacuum laminator or an automatic cutting laminator is used. The heating temperature is preferably, for example, 70℃to 130 ℃. When the photosensitive transfer material includes a protective film described later, the protective film is removed from the photosensitive transfer material, and then the photosensitive transfer material is bonded to an arbitrary member.

Hereinafter, the photosensitive transfer material will be described. The photosensitive transfer material according to an embodiment of the present invention includes a temporary support and a photosensitive resin layer. The photosensitive transfer material according to an embodiment of the present invention may include other layers. Examples of the other layer include a thermoplastic resin layer, an intermediate layer, a refractive index adjusting layer, and a protective film.

A specific example of the layer structure of the photosensitive transfer material is shown below. However, the layer structure of the photosensitive transfer material is not limited to the following specific examples.

(1) Temporary support/photosensitive resin layer/protective film

(2) Temporary support, photosensitive resin layer, refractive index adjustment layer, and protective film

(3) Temporary support/intermediate layer/photosensitive resin layer/protective film

(4) Temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer/protective film

Temporary support

The temporary support in the photosensitive transfer material is a member for supporting a layer such as a photosensitive resin layer, and is finally removed by a peeling process. The temporary support may have a single-layer structure or a multi-layer structure.

The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film that is flexible and does not significantly deform, shrink or elongate under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film. The temporary support is preferably a polyethylene terephthalate film. Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles and scratches.

The temporary support preferably has high transparency in view of being able to perform exposure via the temporary support. The transmittance of the temporary support to 365nm light is preferably 60% or more, more preferably 70% or more.

The temporary support preferably has low haze from the viewpoints of patterning property at the time of exposure through the temporary support and transparency of the temporary support. The haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less.

In view of the patterning property at the time of pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matters, and defects contained in the temporary support be small. The number of particles, foreign matters and defects in the temporary support having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, it is more preferably 3/10 mm ² Hereinafter, it is particularly preferably 0/10 mm ² 。

The thickness of the temporary support is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm, and still more preferably 10 μm to 50 μm, from the viewpoints of ease of handling and versatility. The thickness of the temporary support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation based on SEM (scanning electron microscope: scanning Flectron Microscope).

Examples of the preferable temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16. Mu.m, a biaxially stretched polyethylene terephthalate film having a thickness of 12. Mu.m, and a biaxially stretched polyethylene terephthalate film having a thickness of 9. Mu.m.

In view of imparting handleability, a layer containing fine particles (hereinafter referred to as a "lubricant layer") may be provided on the surface of the temporary support. The lubricant layer may also be provided on one or both sides of the temporary support. The particles contained in the lubricant layer preferably have a diameter of 0.05 μm to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm.

Preferable modes of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-085643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-027363, paragraphs 0041 to 0057 of International publication No. 2012/081δ80, and paragraphs 0029 to 0040 of International publication No. 2018/179370, the contents of which are incorporated herein by reference.

Thermoplastic resin layer-

The photosensitive transfer material preferably includes a thermoplastic resin layer. The thermoplastic resin layer is preferably disposed between the temporary support and the photosensitive resin layer. The manner of the thermoplastic resin layer is described in the above item of "thermoplastic resin layer".

Intermediate layer-

The photosensitive transfer material preferably includes an intermediate layer between the photosensitive resin layer and the thermoplastic resin layer. The manner of the intermediate layer is described in the above item "intermediate layer".

Refractive index adjusting layer

The photosensitive transfer material preferably includes a refractive index adjustment layer. The manner of the refractive index adjustment layer is described in the above item "refractive index adjustment layer".

Protective film-

The photosensitive transfer material may include a protective film. The protective film is preferably disposed on the temporary support via a photosensitive resin layer. That is, the photosensitive transfer material preferably includes a temporary support, a photosensitive resin layer, and a protective film in this order. The protective film is preferably arranged as the outermost layer.

As the protective film, for example, a resin film having heat resistance and solvent resistance can be used. Examples of the protective film include polyolefin films (e.g., polypropylene films and polyethylene films), polyester films (e.g., polyethylene terephthalate films), polycarbonate films, and polystyrene films. As the protective film, a resin film made of the same material as the temporary support may be used. The protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and still more preferably a polyethylene film.

The thickness of the protective film is preferably 1 μm to 100. Mu.m, more preferably 5 μm to 50. Mu.m, still more preferably 5 μm to 40. Mu.m, particularly preferably 15 μm to 30. Mu.m. The thickness of the protective film is preferably 1 μm or more in view of excellent mechanical strength, and preferably 100 μm or less in view of relatively low cost. The thickness of the protective film was calculated as an average value of the thicknesses of 5 portions measured by cross-sectional observation.

The number of fish eyes (fisheyes) having a diameter of 80 μm or more contained in the protective film is preferably 5/m ² The following is given. The "fish eyes" are formed by the entry of foreign substances, undissolved substances, and oxidized degradation substances of a material into a film when the film is produced by a method such as hot melting, kneading, extrusion, biaxial stretching, and cast coating of the material.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² Hereinafter, more preferably 10 pieces/mm ² Hereinafter, more preferably 5 pieces/mm ² The following is given. Can suppress particle generation contained in the protective filmDefects caused by transfer of the irregularities of (a) to the photosensitive resin layer.

From the viewpoint of imparting entanglement, the arithmetic average roughness Ra of the surface of the protective film on the opposite side to the surface in contact with the protective object layer (for example, photosensitive resin layer) is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. The arithmetic average roughness Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

The arithmetic average roughness Ra of the surface of the protective film in contact with the protective layer (for example, the photosensitive resin layer) is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, from the viewpoint of suppressing defects at the time of transfer. The arithmetic average roughness Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

Method for producing photosensitive transfer material

As a method for producing the photosensitive transfer material, for example, a method using the above-described method for forming each layer can be mentioned. For example, a photosensitive resin composition is applied to a temporary support and dried as necessary, whereby a photosensitive resin layer can be formed on the temporary support.

(modification of laminate)

In one embodiment, the laminate may be a photosensitive transfer material including a photosensitive resin layer. That is, in the information providing method according to one embodiment, the photosensitive resin layer included in the photosensitive transfer material may be irradiated with specific light (for example, light having the dominant wavelength λb and light having the dominant wavelength λc). In one embodiment, the laminate may be a laminate described in the following "method for producing a resin pattern".

< method for producing resin Pattern >

The method for manufacturing a resin pattern according to an embodiment of the present invention includes the steps of: preparing a laminate including a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order (hereinafter, sometimes referred to as "preparation step B"); irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of the resin pattern (hereinafter, sometimes referred to as "latent image forming step B"); the photosensitive resin layer is irradiated with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material (hereinafter, sometimes referred to as a "conversion step B"); the region of the photosensitive resin layer exposed to light of the dominant wavelength λb is irradiated with light of the dominant wavelength λc, and fluorescence emitted from the fluorescent material is observed (hereinafter, sometimes referred to as "observation step B"); and developing the photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as "developing step B"). In the above-described method for producing a resin pattern, the dominant wavelength λa and dominant wavelength λb satisfy the relationship λa++λb, the dominant wavelength λa and dominant wavelength λc satisfy the relationship λc > λa, and the dominant wavelength λb and dominant wavelength λc satisfy the relationship λc > λb. As described in the above-mentioned "information providing method", invisible information can be provided to the photosensitive resin layer in the conversion step B, and the invisible information can be visualized in the observation step B. Therefore, according to the above-described embodiment, a method for producing a resin pattern including imparting invisible information to a photosensitive resin layer and visualizing the invisible information can be provided.

The latent image forming step B may be performed simultaneously with the converting step B. The latent image forming step B may be performed between the converting step B and the observing step B. The latent image forming step B may be performed before or after the conversion step B and the observation step B. The method for producing a resin pattern according to one embodiment preferably includes a preparation step B, a latent image forming step B, a conversion step B, an observation step B, and a development step B in this order. The method for producing a resin pattern according to one embodiment preferably includes a preparation step B, a conversion step B, an observation step B, a latent image forming step B, and a development step B in this order.

Main wavelength

The mode of each dominant wavelength is described in the item of the "information providing method" described above. The preferred mode of each dominant wavelength is the same as the preferred mode of each dominant wavelength described in the item of the "information providing method" described above.

Preparation Process B ]

In the preparation step B, a laminate including a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order is prepared.

[ substrate ]

The laminate includes a substrate. The form of the substrate is described in the above item "information providing step". The preferred mode of the substrate is the same as the preferred mode of the substrate described in the item of the "information providing step" described above.

[ conductive layer ]

The laminate includes a conductive layer. The conductive layer is disposed between the substrate and the photosensitive resin layer. The laminate may contain 2 or more conductive layers. In the case where the laminate includes 2 or more conductive layers, the conductive layers may be disposed on both surfaces of the substrate. When the laminate includes 2 or more conductive layers, 2 or more conductive layers may be stacked on one surface of the base material. When the laminate includes 2 or more conductive layers, the material of at least 2 conductive layers is preferably different from each other. The preferred form of the conductive layer is the same as the preferred form of the conductive layer described in the item of the "information imparting step" described above.

The laminate preferably includes at least one of a transparent electrode and a wiring. The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably formed of, for example, a metal oxide film, a metal mesh, or a metal thin wire. Examples of the metal oxide film include ITO (indium tin oxide) and IZO (indium zinc oxide). Examples of the thin metal wire include a silver wire and a copper wire. Silver conductive materials such as silver mesh and silver nanowires are preferred. The detour wiring preferably comprises metal. Examples of the metal in the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and an alloy composed of 2 or more of their metal elements. The metal in the wiring is preferably copper, molybdenum, aluminum, or titanium, and more preferably copper.

[ photosensitive resin layer ]

The laminate includes a photosensitive resin layer. The mode of the photosensitive resin layer is described in the item of the "information imparting method" described above. The preferred embodiment of the photosensitive resin layer is the same as the preferred embodiment of the photosensitive resin layer described in the item of the "information providing method" described above.

[ other layers ]

The laminate may also include other layers. Examples of the other layers include the temporary support, thermoplastic resin layer, intermediate layer, and refractive index adjustment layer described in the above item of "information providing method".

A specific example of the layer structure of the laminate is shown below. However, the layer structure of the laminate is not limited to the following specific examples.

(1) Substrate/conductive layer/photosensitive resin layer

(2) Substrate/conductive layer/photosensitive resin layer/temporary support

(3) Substrate/conductive layer/photosensitive resin layer/thermoplastic resin layer

(4) Substrate/conductive layer/photosensitive resin layer/thermoplastic resin layer/temporary support

(5) Substrate/conductive layer/photosensitive resin layer/intermediate layer/thermoplastic resin layer

(6) Substrate/conductive layer/photosensitive resin layer/intermediate layer/thermoplastic resin layer/temporary support

[ method for producing laminate ]

The method for producing the laminate is not limited. As a method for producing the laminate, for example, a method using the above-described method for forming each layer can be mentioned. As a method for producing the laminate, for example, a method using the photosensitive transfer material described above can be used. For example, by bonding a conductive layer disposed on a substrate and a photosensitive transfer material including a photosensitive resin layer, a laminate including the substrate, the conductive layer, and the photosensitive resin layer in this order can be obtained.

Latent image Forming Process B

In the latent image forming step B, the photosensitive resin layer is irradiated with light having a dominant wavelength λa to form a latent image of the resin pattern. The exposed portion of the negative photosensitive resin layer is patterned in a development step B described later. On the other hand, the non-exposed portion of the positive photosensitive resin layer is patterned in a development step B described later.

The main wavelength λa is described in the above item of the "information providing method". The dominant wavelength λa is determined based on the items described in the item "information giving method" described above.

The light irradiated to the photosensitive resin layer in the latent image forming step B may include a wavelength λa1 other than the dominant wavelength λa, as long as the light does not deviate from the gist of the present invention. When the light irradiated to the photosensitive resin layer in the latent image forming step B includes the wavelength λa1, the wavelength λa1 is preferably determined within a range satisfying a relationship between λa1++λb and λa1++λc. The wavelength λa1 is preferably determined within a range satisfying a relationship of λa1 < λb. The wavelength range of light irradiated to the photosensitive resin layer in the latent image forming step B is preferably less than 410nm. The wavelength range of light irradiated to the photosensitive resin layer in the latent image forming step B is also preferably less than 400nm.

Examples of the light source include various lasers, light emitting diodes, ultra-high pressure mercury lamps, and metal halide lamps.

The exposure is preferably 5mJ/cm ² ～200mJ/cm ² More preferably 10mJ/cm ² ～200mJ/cm ² 。

The light irradiation area is adjusted, for example, according to the target resin pattern. As a method for adjusting the light irradiation region, for example, a method using a photomask having a predetermined light transmitting portion is given. For example, the irradiation region of light can be adjusted by irradiating light through a photomask disposed between the light source and the photosensitive resin layer. Further, by using a light source (for example, laser light) capable of irradiating light having high directivity, the irradiation region of the light can be adjusted.

In the case where the laminate includes a temporary support, light may be irradiated to the photosensitive resin layer through the temporary support. The photosensitive resin layer may be irradiated with light after the temporary support is removed from the laminate. As a method for removing the temporary support, for example, the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of jp 2010-072589 a can be used.

Preferred modes of the light source, the exposure amount and the exposure method used for exposure are described in, for example, paragraphs 0146 to 0147 of International publication No. 2018/155193. The contents of the above publications are incorporated into the present specification by reference.

Conversion Process B

In the conversion step B, the photosensitive resin layer is irradiated with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material. The mode of the conversion step B is the same as the mode of the conversion step a described in the item of the "information providing method" described above. The preferred mode of the conversion step B is the same as the preferred mode of the conversion step a described in the item of the "information providing method" described above. In the case where the laminate includes a temporary support, light may be irradiated to the photosensitive resin layer through the temporary support. The photosensitive resin layer may be irradiated with light after the temporary support is removed from the laminate.

Observation Process B

In the observation step B, the region of the photosensitive resin layer exposed to the light having the dominant wavelength λb is irradiated with light having the dominant wavelength λc, and fluorescence emitted from the fluorescent material is observed. The observation step B is performed in the same manner as the observation step a described in the item of the "information providing method" described above. The preferred mode of the observation step B is the same as the preferred mode of the observation step a described in the item of the "information providing method" described above. In the case where the laminate includes a temporary support, light may be irradiated to the photosensitive resin layer through the temporary support. The photosensitive resin layer may be irradiated with light after the temporary support is removed from the laminate.

Development Process B

In the developing step B, the photosensitive resin layer is developed to form a resin pattern. When the photosensitive resin layer is a negative photosensitive resin layer, the non-exposed portion in the latent image forming step B is removed, and the exposed portion in the latent image forming step B forms a resin pattern. When the photosensitive resin layer is a positive photosensitive resin layer, the exposed portion in the latent image forming step B is removed, and the non-exposed portion in the latent image forming step B is formed into a resin pattern.

The photosensitive resin layer is developed using, for example, a developer. The developer is preferably an aqueous alkaline solution. Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide). The preferred developer is, for example, one described in paragraph 0194 of International publication No. 2015/093271.

Examples of the development include spin-coating immersion development, shower development, spin development, and immersion development. The preferable development method is, for example, the development method described in paragraph 0195 of international publication No. 2015/093271.

Other procedures

When the photosensitive resin layer is a negative photosensitive resin layer, the method for producing a resin pattern according to an embodiment of the present invention may include at least one of a step of exposing the resin pattern obtained in the development step B (hereinafter, referred to as a "post-exposure step") and a step of heating the resin pattern obtained in the development step B (hereinafter, referred to as a "post-baking step"). In the case where the method for producing a resin pattern according to an embodiment of the present invention includes both the post-exposure step and the post-baking step, the post-baking step is preferably performed after the post-exposure step.

The exposure amount in the post-exposure step is preferably 100mJ/cm ² ～5,000mJ/cm ² More preferably 200mJ/cm ² ～3,000mJ/cm ² . The heating temperature in the post-baking step is preferably 80 to 250 ℃, more preferably 90 to 160 ℃. The heating time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

Use of resin Pattern

The resin pattern is used, for example, as a permanent film or a protective film in etching treatment. The permanent film is used, for example, as a protective film for the conductive layer. The resin pattern is preferably used as a protective film in the etching process. For example, in the method for manufacturing the circuit wiring, after the resin pattern is formed on the conductive layer, the conductive layer not covered with the resin pattern is removed by etching treatment, so that the desired circuit wiring can be formed.

< method for producing Circuit Wiring >

A method for manufacturing a circuit wiring according to an embodiment of the present invention includes the steps of: preparing a laminate including a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order (hereinafter, sometimes referred to as "preparation step C"); irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of the resin pattern (hereinafter, sometimes referred to as "latent image forming step C"); the photosensitive resin layer is irradiated with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material (hereinafter, sometimes referred to as "conversion step C"); the region of the photosensitive resin layer exposed to light of the dominant wavelength λb is irradiated with light of the dominant wavelength λc, and fluorescence emitted from the fluorescent material is observed (hereinafter, sometimes referred to as "observation step C"); developing the photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as "developing step C"); and etching the conductive layer in the region where the resin pattern is not arranged to form a circuit wiring (hereinafter, sometimes referred to as "etching process C"). In the above-described method for manufacturing a circuit wiring, the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa++λb, the dominant wavelength λa and the dominant wavelength λc satisfy the relationship λc > λa, and the dominant wavelength λb and the dominant wavelength λc satisfy the relationship λc > λb. As described in the above-mentioned item of the "information imparting method", invisible information can be imparted to the photosensitive resin layer in the conversion step C, and the invisible information can be visualized in the observation step C. Therefore, according to the above-described embodiment, a method for manufacturing a circuit wiring including giving invisible information to a photosensitive resin layer and visualizing the invisible information can be provided.

The latent image forming step C may be performed simultaneously with the conversion step C. The latent image forming step C may be performed between the converting step C and the observing step C. The latent image forming step C may be performed before or after the conversion step C and the observation step C. The method for manufacturing a touch panel according to one embodiment preferably includes a preparation step C, a latent image forming step C, a conversion step C, an observation step C, a development step C, and an etching step C in this order. The method for manufacturing a circuit wiring according to one embodiment preferably includes a preparation step C, a conversion step C, an observation step C, a latent image forming step C, a development step C, and an etching step C in this order.

Preparation Process C

The preparation step C is performed in the same manner as the preparation step B described in the item "method for producing a resin pattern" above. The preferred mode of the preparation step C is the same as the preferred mode of the preparation step B described in the item of the "information providing method" described above.

Latent image Forming Process C

The method of the latent image forming step C is the same as the method of the latent image forming step B described in the item of the "method of manufacturing a resin pattern" described above. The preferred embodiment of the latent image forming step C is the same as the preferred embodiment of the latent image forming step B described in the item "method for producing a resin pattern" above.

Conversion Process C

The mode of the conversion step C is the same as the mode of the conversion step B described in the item of the "method for producing a resin pattern" described above. The preferred mode of the conversion step C is the same as the preferred mode of the conversion step B described in the item of the "method for producing a resin pattern" described above.

Observation procedure C

The method of the observation step C is the same as the method of the observation step B described in the item of the "method of manufacturing a resin pattern" described above. The preferred embodiment of the observation step C is the same as the preferred embodiment of the observation step B described in the item of the "method for producing a resin pattern" described above.

Development Process C

The development step C is performed in the same manner as the development step B described in the item "method for producing a resin pattern" above. The preferred mode of the developing step C is the same as the preferred mode of the developing step B described in the item of the "method for producing a resin pattern" described above.

< etching Process >

In the etching step, the conductive layer located in the region where the resin pattern is not arranged is subjected to etching treatment to form a circuit wiring. The "conductive layer located in a region where the resin pattern is not arranged" specifically means a conductive layer not covered with the resin pattern. In the etching step, the conductive layer not covered with the resin pattern is removed by etching, and the circuit wiring is formed by the conductive layer remaining after the etching.

Examples of the method of the etching treatment include the method described in paragraphs 0209 to 0210 of Japanese patent application laid-open No. 2017-120435 and the method described in paragraphs 0048 to 0054 of Japanese patent application laid-open No. 2010-152155. As a method of etching treatment, for example, a wet etching method in which the substrate is immersed in an etching liquid can be cited. As a method of etching treatment, for example, a method based on dry etching such as plasma etching can be cited.

The type of the etching liquid used in the wet etching is selected, for example, according to the object of the etching process. Examples of the etching liquid include an acidic or alkaline etching liquid.

Examples of the acidic etching liquid include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid. Examples of the acidic etching solution include a mixed aqueous solution of the above-mentioned acidic component and a salt selected from ferrous chloride, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components.

Examples of the alkaline etching liquid include aqueous solutions of alkali components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (for example, tetramethylammonium hydroxide). As the alkaline etching liquid, for example, a mixed aqueous solution of the above-mentioned alkali component and a salt (for example, potassium permanganate) can be cited. The alkali component may be a component obtained by combining a plurality of alkali components.

Removal Process

The method for manufacturing a circuit wiring according to an embodiment of the present invention preferably includes a step of removing the remaining resin pattern (hereinafter referred to as "removing step"). The removal step is preferably performed after the etching step.

As a removal method, for example, chemical treatment is given. In the removing step, the remaining resin pattern is preferably removed using a removing liquid. Examples of the method using the removing liquid include a method of immersing a substrate having a residual resin pattern in a removing liquid under stirring having a temperature of preferably 30 to 80 ℃ and more preferably 50 to 80 ℃ for 1 to 30 minutes.

Examples of the removing liquid include a removing liquid obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

In the removal step, the remaining resin pattern may be removed by a known method such as a spray method, a shower method, or a spin-coating immersion method using a removal liquid.

Other procedures

The method for manufacturing a circuit wiring according to an embodiment of the present invention may further include other steps. Examples of the other steps include a step of reducing the reflectance of visible light as described in paragraph 0172 of international publication No. 2019/022089 and a step of forming a new conductive layer on an insulating film as described in paragraph 0172 of international publication No. 2019/022089.

The method for manufacturing a circuit wiring according to an embodiment of the present invention may further include a step of performing a treatment for reducing the visible ray reflectance of a part or all of the conductive layer. As the treatment for reducing the reflectance of visible light, for example, an oxidation treatment is given. When the conductive layer contains copper, the visible ray reflectance of the conductive layer can be reduced by oxidizing copper to produce copper oxide and blackening the conductive layer. Treatments for reducing the reflectance of visible light are described in paragraphs 0017 to 0025 of Japanese patent application laid-open No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese patent application laid-open No. 2013-206315. The contents described in these publications are incorporated into the present specification by reference.

The method for manufacturing a circuit wiring according to an embodiment of the present invention preferably includes a step of forming an insulating film on a surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed. As a step of forming the insulating film, for example, a known method of forming a permanent film is given. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material. In the step of forming a new conductive layer on the insulating film, for example, a photosensitive material having conductivity may be used, and a new conductive layer having a desired pattern may be formed by photolithography.

In the method for manufacturing a circuit wiring according to an embodiment of the present invention, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of a base material, and to form a circuit sequentially or simultaneously with respect to the conductive layers formed on both surfaces of the base material. Through the above steps, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a base material and a second conductive pattern is formed on the other surface of the base material can be formed. The circuit wiring for a touch panel having the above-described structure is preferably formed from both surfaces of the base material in a roll-to-roll manner.

< use of Circuit Wiring >

The circuit wiring manufactured by the method for manufacturing a circuit wiring according to an embodiment of the present invention can be applied to various devices. Examples of the device having the circuit wiring include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic EL display device or a liquid crystal display device.

< method for manufacturing touch Panel >

A method for manufacturing a touch panel according to an embodiment of the present invention includes the steps of: preparing a laminate including a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order (hereinafter, sometimes referred to as "preparation step D"); irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of the resin pattern (hereinafter, sometimes referred to as "latent image forming step D"); the photosensitive resin layer is irradiated with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material (hereinafter, sometimes referred to as a "conversion step D"); the region of the photosensitive resin layer exposed to light of the dominant wavelength λb is irradiated with light of the dominant wavelength λc, and fluorescence emitted from the fluorescent material is observed (hereinafter, sometimes referred to as "observation step D"); developing the photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as "developing step D"); and etching the conductive layer in the region where the resin pattern is not arranged to form a wiring for a touch panel (hereinafter, sometimes referred to as "etching process D"). In the above-described method for manufacturing a touch panel, the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa++λb, the dominant wavelength λa and the dominant wavelength λc satisfy the relationship λc > λa, and the dominant wavelength λb and the dominant wavelength λc satisfy the relationship λc > λb. As described in the above-mentioned item of the "information imparting method", invisible information can be imparted to the photosensitive resin layer in the conversion step D, and the invisible information can be visualized in the observation step D. Therefore, according to the above-described embodiment, a method for manufacturing a touch panel including giving invisible information to a photosensitive resin layer and visualizing the invisible information can be provided.

The latent image forming step D may be performed simultaneously with the conversion step D. The latent image forming step D may be performed between the converting step D and the observing step D. The latent image forming step D may be performed before or after the conversion step D and the observation step D. The method for manufacturing a touch panel according to one embodiment preferably includes a preparation step D, a latent image forming step D, a conversion step D, an observation step D, a development step D, and an etching step D in this order. The method for manufacturing a touch panel according to one embodiment preferably includes a preparation step D, a conversion step D, an observation step D, a latent image forming step D, a development step D, and an etching step D in this order.

The method of manufacturing a circuit wiring according to an embodiment of the present invention is similar to the method of manufacturing a circuit wiring described in the above-described "method of manufacturing a circuit wiring" except that a wiring for a touch panel is formed in the etching process step D. The matters described in the above "method for manufacturing a circuit wiring" are referred to in the method for manufacturing a touch panel according to an embodiment of the present invention.

Examples of patterns of a photomask used for manufacturing a wiring for a touch panel include pattern a and pattern B described in japanese patent application laid-open publication No. 2019-204070. For forming the constituent elements of the touch panel other than the wiring, a known method for manufacturing the touch panel may be referred to.

Examples of the detection method of the touch panel include a resistive touch method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include an embedded type (for example, a structure described in fig. 5, 6, 7, and 8 of japanese patent application laid-open No. 2012-517051), an externally embedded type (for example, a structure described in fig. 19 of japanese patent application laid-open No. 2013-168125, and a structure described in fig. 1 and 5 of japanese patent application laid-open No. 2012-89102), an OGS (One Glass Solution: monolithic glass Touch technology), a TOL (Touch-on-Lens: overlay Touch) type (for example, a structure described in fig. 2 of japanese patent application laid-open No. 2013-54727), and various externally hung types (for example, GG, g1·g2, GFF, GF1, and G1F) and other structures (for example, a structure described in fig. 6 of japanese patent application laid-open No. 2013-164871).

Examples

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, use amounts, proportions, processing contents, and processing steps) of the embodiments shown below may be appropriately changed within the scope of the object of the present invention.

< short for short >

The terms shown below have the following meanings, respectively.

A-1: copolymers of styrene, methacrylic acid and methyl methacrylate (monomer ratio=48 mass%: 29 mass%: 23 mass%, mw:60,000, polymer A)

A-2: propylene glycol monomethyl ether acetate solution containing benzyl methacrylate, methacrylic acid and acrylic acid copolymer (monomer ratio=70 mass%: 15 mass%, solid content concentration: 30.0 mass%, mw:30,000, acid value: 153 mgKOH/g)

A-3: kuraray Poval PVA-205 (Kuraray Co., ltd.)

A-4: polyvinylpyrrolidone K-30 (NIPPON SHOKUBIAI CO., LTD.)

B-1: BPE-500 (Shin Nakamura Chemical Co., ltd., polymerizable Compound)

B-2: dimethacrylates (polymerizable compounds) of polyethylene glycol to which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide were added at both ends of bisphenol A

B-3: m-270 (TOAGOSEI CO., LTD. Polymerizable Compound)

B-4: A-TMPT (Shin Nakamura Chemical Co., ltd., polymerizable Compound)

B-5: SR-454 (polymerizable Compound manufactured by Arkema Co., ltd.)

B-6: A-9300-CL1 (Shin Nakamura Chemical Co., ltd., polymerizable Compound)

B-7: NK esters A-DCP (Shin Nakamura Chemical Co., ltd., polymerizable Compound)

B-8:8UX-015A (Taisei Fine Chemical Co., ltd., polymerizable Compound)

B-9: ARONIX TO-2349 (TOAGOSEI CO., LTD. Polymerizable Compound)

B-10: ARUFON UC-3510 (TOAGOSEI co., ltd. Polymerizable compound)

C-1: B-CIM (KUROGANE KASEI Co., ltd., polymerization initiator)

C-2: SB-PI 701 (Sanyo transfer Co., ltd., polymerization initiator)

D-1: TDP-G (Kawaguchi Chemical Industry Co., LTD.)

D-2: irganox245 (manufactured by BASF corporation)

D-3: n-nitrosophenyl hydroxylamine aluminum salt (FUJIFILM Wako PureChemical Corporation system)

E-1: colorless crystal violet (Tokyo Chemical Industry co., ltd., fluorescent material precursor)

E-2: n-phenylglycine (Tokyo Chemical Industry Co., ltd.)

E-3: bright green (TokyoChemical Industry Co., ltd.)

E-4: CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD)

E-5: mixtures of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole with 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole (Gu Liang:1=1:1)

E-6: phenanthrone (Tokyo Chemical Industrial Co., ltd.)

E-7: f-552 (DIC CORPORATION)

E-8: f-444 (DIC CORPORATION)

F-1: methyl ethyl ketone (SANKYO CHEMICAL Co., ltd.)

F-2: propylene glycol monomethyl ether acetate (SHOWA DENKO K.K.)

F-3: ion exchange water

F-4: methanol (Mitsubishi Gas Chemical Company, inc. made)

< preparation of thermoplastic resin composition >

(thermoplastic resin composition 1)

The following components were mixed to prepare a thermoplastic resin composition 1.

A-2:42.85 parts by mass

B-7:4.63 parts by mass

B-8:2.31 parts by mass

B-9:0.77 part by mass

E-7:0.03 part by mass

F-1:39.50 parts by mass

F-2:9.51 parts by mass

A compound having the structure shown below (a photoacid generator synthesized by the method described in paragraph 0227 of Japanese patent application laid-open No. 2013-47765): 0.32 part by mass

[ chemical formula 4]

A compound having the structure shown below (a dye that develops color by an acid): 0.08 part by mass

[ chemical formula 5]

(thermoplastic resin composition 2)

The following components were mixed to prepare a thermoplastic resin composition 2.

A-2:38.42 parts by mass

B-10:8.89 parts by mass

C-1:3.00 parts by mass

C-2:0.15 part by mass

E-1:0.50 part by mass

E-7:0.03 part by mass

F-1:39.50 parts by mass

F-2:9.51 parts by mass

< preparation of composition for Forming intermediate layer >

The following components were mixed to prepare a composition for forming an intermediate layer.

A-3:3.22 parts by mass

A-4:1.49 parts by mass

E-8:0.0015 part by mass

F-3:38.12 parts by mass

F-4:57.17 parts by mass

< preparation of photosensitive resin composition >

Photosensitive resin compositions were prepared according to the descriptions in table 1. The unit of the addition amount of each component in table 1 is parts by mass.

TABLE 1

Photosensitive resin composition	1	2	3	A
					A-1	50.00	50.00	51.00	50.40
B-1	36.20	27.10	15.00	36.20
					B-2	-	-	10.00	-
B-3	5.00	3.11	-	5.00
					B-4	-	5.00	5.00	-
B-5	-	6.12	5.00	-
					B-6	-	-	9.77	-
C-1	6.99	6.95	3.00	6.99
					C-2	0.50	0.49	0.30	0.50
D-1	0.31	0.23	-	0.31
					D-2	-	-	0.20	-
D-3	-	-	0.01	-
					E-1	0.40	0.30	0.60	-
E-2	0.20	0.20	-	0.20
					E-3	-	-	0.10	-
E-4	0.10	0.10	-	0.10
					E-5	-	-	0.10	-
E-6	0.01	0.01	-	0.01
					E-7	0.29	0.29	-	0.29
F-1	396.00	396.00	396.00	396.00
					F-2	170.00	170.00	170.00	170.00

Example 1]

(production of photosensitive transfer Material 1)

As a temporary support, a polyethylene terephthalate film having a thickness of 30 μm was prepared. The thermoplastic resin composition 1 was applied to the surface of the temporary support using a slit nozzle so that the width of the coating became 1.0m and the thickness after drying became 4.0. Mu.m. The thermoplastic resin composition 1 was dried at 80℃for 40 seconds, thereby forming a thermoplastic resin layer. The composition for forming an intermediate layer was applied to the surface of the thermoplastic resin layer by using a slit nozzle so that the width of the coating was 1.0m and the thickness after drying was 1.2. Mu.m. The intermediate layer-forming composition was dried at 80 ℃ for 40 seconds, thereby forming an intermediate layer. The photosensitive resin composition 1 was applied to the surface of the intermediate layer using a slit nozzle so that the coating width was 1.0m and the thickness after drying was 3.0 μm. The photosensitive resin composition 1 was dried at 80 ℃ for 40 seconds, thereby forming a photosensitive resin layer. A polyethylene terephthalate film (manufactured by TORAY INDUSTRIES, INC., lumirror16QS 62) was pressure-bonded to the surface of the photosensitive resin layer as a protective film, thereby producing a photosensitive transfer material 1. The photosensitive transfer material 1 is a photoresist material that can be patterned by exposure to 365nm light having a dominant wavelength λa.

(lamination)

A substrate comprising a polyethylene terephthalate film having a thickness of 100 μm as a base material and a copper layer having a thickness of 200nm as a conductive layer was prepared. In the formation of the conductive layer, a sputtering method is used. After the protective film was peeled off from the photosensitive transfer material 1, the substrate and the photosensitive transfer material 1 were bonded using a sheet laminator under the following conditions. The obtained laminate comprises, in order, a polyethylene terephthalate film, a copper layer, a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support.

Roller temperature: 100 DEG C

Lamination speed: 2 m/min

Lamination pressure: 0.5MPa

(giving of information)

A photomask provided with a 9-bit digital pattern is disposed as a light transmitting portion on a temporary support of the laminate. In the photomask, a total of 10 sets of digital patterns were provided. In the total 10 groups of digital patterns, the number is from a digital pattern with a thickness of 100 μm to a digital pattern with a thickness of 10 μm, and the thickness of the digital pattern is 10 μmThe units change. A filter (Asahi Spectra co., ltd., HMZ 0405) was placed on the photomask. The filter (HMZ 0405) transmits only light around 405 nm. The laminate was exposed to light via a filter using a high-pressure mercury lamp. The energy in the exposure was 200mJ/cm ² 。

(evaluation of visibility)

The region where the digital pattern was exposed was irradiated with green reference light having a dominant wavelength λc of 530nm using a light source (manufactured by OPTOCODE CORPORATION, LED 530-3W), and the generated fluorescence was visually observed with a 10-fold magnifying glass via a long-pass filter (manufactured by FUJIFILM Corporation, SC 62). Visibility was evaluated according to the following criteria. The evaluation results are shown in table 2.

A: the number of 30 μm thick and thin can be visually recognized.

B: the 60 μm thick and thin number can be visually recognized.

C: the numbers of 100 μm thick and thin cannot be visually recognized or all the numbers cannot be visually recognized.

< examples 2 to 4>

Visibility was evaluated by the same procedure as in example 1, except that the types of the photosensitive resin composition and the thermoplastic resin composition were appropriately changed according to the descriptions in tables 1 and 2. The evaluation results are shown in table 2.

Comparative example 1 ]

The laminate was exposed by the same procedure as in example 1 except that the filter (Asahi Spectra co., ltd. Manufactured by HMZ 0405) was changed to the filter (Asahi Spectra co., ltd. Manufactured by LX 0365). The filter (Asahi Spectra co., ltd. LX 0365) transmits only light around 365 nm. The wavelength of 365nm is a wavelength used for patterning the photosensitive resin layer. In comparative example 1, the digital pattern can be visually recognized by using a magnifying glass without irradiating reference light. The above results are not suitable for use for hiding information.

Comparative example 2]

Visibility was evaluated in the same manner as in example 1 except that the light source of the reference light was changed to an LED lamp (manufactured by OPTOCODE CORPORATION, LED-UV385P, dominant wavelength λc:385 nm). The evaluation results are shown in table 2.

Comparative example 3 ]

Visibility was evaluated by the same procedure as in example 1 except that the types of the photosensitive resin compositions were changed as shown in tables 1 and 2. The evaluation results are shown in table 2.

TABLE 2

	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3
								Thermoplastic resin composition	1	1	1	2	1	1	1
Photosensitive resin composition	1	2	3	1	1	1	A
								λa[nm]	365	365	365	365	365	365	365
λb[nm]	405	405	405	405	365	405	405
								λc[nm]	530	530	530	530	-	385	530
Visibility of	A	A	B	B	-	C	C

In examples 1 to 4, the hidden digital pattern was visually recognized by fluorescence. On the other hand, in comparative example 1, the digital pattern could be visually recognized without reference light, and the digital pattern could not be hidden. The results are indicated by "-" in Table 2. In comparative example 2, the dominant wavelength λc of the reference light is shorter than the dominant wavelength λb for imparting the digital pattern, so-called "fogging" of the digital pattern occurs, and the digital pattern cannot be sufficiently visually recognized. Here, "fogging" means that the film portion including the given digital pattern is exposed in advance by the reference light, and thus the exposed portion and the unexposed portion of the digital pattern are both sensitized, and the digital pattern cannot be clearly recognized. In comparative example 3, since the photosensitive resin layer does not contain a fluorescent material precursor, the digital pattern cannot be visually recognized by fluorescence.

Example 5 ]

The photosensitive transfer material 1 used in example 1 was used for the following evaluation.

(lamination)

A substrate comprising a polyethylene terephthalate film having a thickness of 100 μm as a base material and a copper layer having a thickness of 200nm as a conductive layer was prepared. In the formation of the conductive layer, a sputtering method is used. After the protective film was peeled off from the photosensitive transfer material 1, the substrate and the photosensitive transfer material 1 were bonded using a sheet laminator under the following conditions. The obtained laminate comprises, in order, a polyethylene terephthalate film, a copper layer, a photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support.

Roller temperature: 100 DEG C

Lamination speed: 2 m/min

Lamination pressure: 0.5MPa

(formation of latent image of resin Pattern)

A photomask having a line-and-space pattern of 20 μm/20 μm was arranged on a temporary support and a high-pressure mercury lamp was used at 100mJ/cm ² The laminate obtained by lamination was exposed to light. The photomask has a design smaller than the size of the laminate so that the peripheral portion of the laminate is not exposed.

(giving of information)

A photomask provided with a 9-bit digital pattern is disposed as a light transmitting portion on a temporary support of the laminate. The digital pattern of the photomask is arranged on the peripheral portion of the laminate on which the latent image of the resin pattern is not formed. In the photomask, a total of 10 sets of digital patterns were provided. Among the total 10 sets of digital patterns, the digital pattern with a thickness of 100 μm was changed to the digital pattern with a thickness of 10 μm, and the thickness of the digital pattern was changed in units of 10 μm. A filter (Asahi Spectra co., ltd., HMZ 0405) was placed on the photomask. The filter (HMZ 0405) transmits only light around 405 nm. The laminate was exposed to light via a filter using a high-pressure mercury lamp. The energy in the exposure was 200mJ/cm ² 。

(evaluation of visibility)

The region where the digital pattern was exposed was irradiated with green reference light having a dominant wavelength λc of 530nm using a light source (manufactured by OPTOCODE CORPORATION, LED 530-3W), and the generated fluorescence was visually observed with a 10-fold magnifying glass via a long-pass filter (manufactured by FUJIFILM Corporation, SC 62). The digital pattern of 30 μm thickness can be visually recognized.

(development)

After the visibility was evaluated, the temporary support was peeled off and developed with a 0.9 mass% sodium carbonate aqueous solution at 25 ℃ for 30 seconds, to prepare a resin pattern having a line-space pattern of 20 μm/20 μm. The light irradiated in the visibility evaluation did not cause fogging, and a resin pattern having a good shape could be produced.

The disclosure of japanese patent application 2020-165597, filed on even 30 months of 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 were specifically and individually indicated to be incorporated by reference.

Claims (10)

1. An information providing method for providing identifiable information to a photosensitive resin layer on which a latent image of a resin pattern is formed by exposure to light having a dominant wavelength λa,

The information giving method includes the steps of:

irradiating a photosensitive resin layer containing a fluorescent material precursor with light having a dominant wavelength lambdab to convert the fluorescent material precursor into a fluorescent material; and

Irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having the dominant wavelength λc, observing fluorescence emitted from the fluorescent material,

the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa noteq λb,

the dominant wavelength λa and the dominant wavelength λc satisfy the relationship of λc > λa,

the dominant wavelength λb and the dominant wavelength λc satisfy the relationship of λc > λb.

2. The information providing method according to claim 1, wherein,

observing the fluorescence includes observing the fluorescence via a filter that blocks the dominant wavelength λc.

3. The information providing method according to claim 1 or 2, wherein,

the dominant wavelength λa and the dominant wavelength λb satisfy the relationship of λb > λa.

4. The information providing method according to any one of claims 1 to 3, wherein,

the dominant wavelength λa is less than 400nm, the dominant wavelength λb is more than 400nm and less than 500nm, and the dominant wavelength λc is more than 500nm and less than 700nm.

5. The information providing method according to any one of claims 1 to 4, wherein,

The fluorescent material precursor is a compound having a triarylmethane structure.

6. The information providing method according to any one of claims 1 to 5, wherein,

the fluorescent material precursor is a leuco dye.

7. The information providing method according to any one of claims 1 to 6, wherein,

the photosensitive resin layer includes a polymer, a polymerizable compound, and a polymerization initiator.

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

preparing a laminate comprising a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order;

irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of a resin pattern;

irradiating the photosensitive resin layer with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material;

irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having a dominant wavelength λc, and observing fluorescence emitted from the fluorescent material; and

Developing the photosensitive resin layer to form a resin pattern,

the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa noteq λb,

the dominant wavelength λa and the dominant wavelength λc satisfy the relationship of λc > λa,

The dominant wavelength λb and the dominant wavelength λc satisfy the relationship of λc > λb.

9. A method of manufacturing a circuit wiring, comprising the steps of:

preparing a laminate comprising a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order;

irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of a resin pattern;

irradiating the photosensitive resin layer with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material;

irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having a dominant wavelength λc, and observing fluorescence emitted from the fluorescent material;

developing the photosensitive resin layer to form a resin pattern; and

Etching the conductive layer in a region where the resin pattern is not arranged to form a circuit wiring,

the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa noteq λb,

the dominant wavelength λa and the dominant wavelength λc satisfy the relationship of λc > λa,

the dominant wavelength λb and the dominant wavelength λc satisfy the relationship of λc > λb.

10. A method of manufacturing a touch panel, comprising the steps of:

preparing a laminate comprising a base material, a conductive layer, and a photosensitive resin layer containing a fluorescent material precursor in this order;

Irradiating the photosensitive resin layer with light having a dominant wavelength λa to form a latent image of a resin pattern;

irradiating the photosensitive resin layer with light having a dominant wavelength λb to convert the fluorescent material precursor into a fluorescent material;

irradiating a region of the photosensitive resin layer exposed to the light having the dominant wavelength λb with light having a dominant wavelength λc, and observing fluorescence emitted from the fluorescent material;

developing the photosensitive resin layer to form a resin pattern; and

Etching the conductive layer in a region where the resin pattern is not arranged to form a wiring for a touch panel,

the dominant wavelength λa and the dominant wavelength λb satisfy the relationship λa noteq λb,

the dominant wavelength λa and the dominant wavelength λc satisfy the relationship of λc > λa,

the dominant wavelength λb and the dominant wavelength λc satisfy the relationship of λc > λb.