KR102595962B1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board - Google Patents

Abstract

(A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: at least one member selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof. A photopolymerization initiator containing a photopolymerization initiator, and component (D): a nitroxyl compound, wherein the component (D) includes a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure. Photosensitive resin composition.

Description

Photosensitive resin composition, photosensitive element, method of forming a resist pattern, and method of manufacturing a printed wiring board {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT, METHOD FOR FORMING RESIST PATTERN, AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

This disclosure relates to a photosensitive resin composition, a photosensitive element, a method of forming a resist pattern, and a method of manufacturing a printed wiring board.

In the field of manufacturing printed wiring boards, photosensitive resin compositions are widely used as resist materials used for etching or plating. The photosensitive resin composition is often used as a photosensitive element (laminated body) including a support and a layer formed on the support using the photosensitive resin composition (hereinafter also referred to as “photosensitive resin composition layer”).

A printed wiring board is manufactured as follows, for example. First, a photosensitive element having a support and a photosensitive resin composition layer is prepared, and the photosensitive resin composition layer of the photosensitive element is formed on a circuit forming substrate (photosensitive layer forming step). Next, after peeling and removing the support, actinic light is irradiated to a predetermined portion of the photosensitive resin composition layer to cure the exposed portion (exposure process). Thereafter, a resist pattern, which is a cured product of the photosensitive resin composition (hereinafter also referred to as “resist cured product”), is formed on the substrate by removing (developing) the unexposed portion from the substrate (development step). Next, the substrate on which the resist pattern is formed is subjected to etching or plating to form a circuit on the substrate (circuit formation process), and then the resist is finally peeled off to manufacture a printed wiring board (peeling process).

As a method of exposure, a method of exposing through a photomask using a mercury lamp as a light source has been conventionally used. In addition, recently, a direct drawing exposure method called DLP (Digital Light Processing) or LDI (Laser Direct Imaging), which draws directly on the photosensitive resin composition layer without going through a photomask based on digital data of the pattern, has been proposed. This direct drawing exposure method is being introduced for the production of high-density package substrates because it has better alignment accuracy than the exposure method using a photomask and can obtain high-precision patterns.

In general, in the exposure process, it is desired to shorten the exposure time to improve production efficiency. However, in the above-described direct drawing exposure method, in addition to using monochromatic light such as a laser as a light source, actinic light is irradiated while scanning the substrate, so a long exposure time is required compared to the conventional exposure method using a photomask. tends to require. Therefore, in order to shorten the exposure time and increase production efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition more than before.

Meanwhile, with the recent increase in the density of printed wiring boards, the demand for photosensitive resin compositions capable of forming resist patterns with excellent resolution and adhesion is increasing. In particular, in the manufacture of package substrates, a photosensitive resin composition capable of forming a resist pattern with L/S (line width/space width) of 10/10 (unit: ㎛) or less is required. Therefore, there is a strong demand to improve resolution and adhesion even by 1 μm.

Additionally, various photosensitive resin compositions have conventionally been examined. Patent Document 1 discloses a photosensitive resin composition containing a phenol-based compound as a polymerization inhibitor. In addition, for example, several proposals have been made regarding photosensitive resin compositions using stable radicals such as spin trap agents or nitroxyl compounds (for example, see Patent Documents 2 to 5).

Patent Document 1: Japanese Patent Publication No. 2000-162767 Patent Document 2: Japanese Patent Publication No. 2003-140329 Patent Document 3: Japanese Patent Publication No. 2003-215790 Patent Document 4: Japanese Patent Publication No. 2006-11397 Patent Document 5: Japanese Patent Publication No. 2007-133398

However, while the photosensitive resin composition described in Patent Document 1 improves resolution by containing a polymerization inhibitor, radical polymerization is delayed and sufficient sensitivity may not be obtained. The photosensitive resin compositions described in Patent Documents 2 to 5 sometimes cannot be said to sufficiently satisfy sensitivity, resolution, and adhesion when used as resists for printed wiring boards. That is, in the conventional photosensitive resin composition, there is still room for improvement in terms of improving resolution and adhesion while maintaining sensitivity during resist pattern formation.

In addition, with respect to the photosensitive resin composition layer for forming a resist pattern, reduction of residue at the bottom of the resist (also referred to as "resist skirt" or "sleeping") is also required. The residue (resist hem) at the bottom of the resist is generated when the bottom of the resist spreads due to swelling during the development process and does not peel off from the substrate even when drying. When plating is performed, if a large amount of resist seam is generated, the contact area between the plating and the substrate becomes small, which causes a decrease in the mechanical strength of the formed circuit. The influence of this resist fringe increases as the circuit formation of the printed wiring board becomes more refined. Especially when forming a circuit with an L/S of 10/10 (unit: ㎛) or less, if the amount of resist fringe generated is large, the circuit formation itself after plating will be damaged. It can be difficult. Additionally, when etching is performed, if the amount of resist fringes is large, the contact area between the etchant and the substrate becomes small, making it difficult to form a conductor pattern as designed. Additionally, when etching is performed, if a large amount of resist seam is generated, the imbalance in the width of the conductor pattern increases, which may affect product yield. Therefore, there is a demand for a photosensitive resin composition that can form a resist pattern with a smaller amount of resist fringing.

The present disclosure provides a photosensitive resin composition capable of forming a resist pattern with excellent resolution and adhesion and with a reduced amount of resist fringing with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and the production of a printed wiring board. The purpose is to provide a method.

As a result of careful study to solve the above problem, by combining a binder polymer, a photopolymerizable compound, 2,4,5-triarylimidazole dimer or a derivative thereof, and a specific nitroxyl compound, It was discovered that a photosensitive resin composition that has excellent resolution and adhesion and can form a resist pattern with a reduced amount of resist fringing with excellent sensitivity can be obtained.

That is, one embodiment of the present disclosure includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: 2,4,5-triarylimidazole dimer and derivatives thereof. A photopolymerization initiator containing at least one member selected from the group consisting of a component (D): a nitroxyl compound, wherein the component (D) is 2,2,6,6-tetramethylpiperidine-1. -Provides a photosensitive resin composition containing a compound having an oxyl structure.

The 2,4,5-triarylimidazole dimer and its derivatives may include a compound represented by the following general formula (1).

[In formula (1), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group that may be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5. However, when p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different.]

The component (A) may have a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylic acid.

The photosensitive resin composition of one embodiment of the present disclosure may further contain (E) component: phenol-based compound.

The photosensitive resin composition of one embodiment of the present disclosure further contains component (F): a sensitizer, and the component (F) may contain a pyrazoline compound.

Another embodiment of the present disclosure also provides a photosensitive element including a support and a photosensitive resin composition layer formed using the photosensitive resin composition provided on the support. By using such a photosensitive element, a resist pattern with particularly excellent resolution and adhesion and with a reduced amount of resist fringe generation can be efficiently formed with excellent sensitivity.

Another embodiment of the present disclosure also provides a photosensitive layer forming process of forming a photosensitive resin composition layer on a substrate using the photosensitive resin composition or the photosensitive element, and an active layer in at least a portion of the photosensitive resin composition layer. An exposure process of irradiating light to photocure the area to form a cured area, and removing a region other than the cured area of the photosensitive resin composition layer from the substrate to form a cured area on the substrate. A method of forming a resist pattern having a developing process for forming a phosphor resist pattern is provided. According to this forming method, a resist pattern with excellent resolution and adhesion and with a reduced amount of resist fringe generation can be efficiently formed with excellent sensitivity.

In the above resist pattern formation method, the wavelength of the actinic light to be irradiated may be within the range of 340 nm to 430 nm. As a result, a resist pattern with better resolution and adhesion and with a reduced amount of resist fringing can be more efficiently formed with excellent sensitivity.

Another embodiment of the present disclosure also provides a method of manufacturing a printed wiring board including a process of etching or plating a substrate on which a resist pattern is formed by the resist pattern forming method. According to this manufacturing method, a printed wiring board with high-density wiring, such as a high-density package board, can be manufactured efficiently, with excellent precision, and with good productivity.

According to the present disclosure, a photosensitive resin composition capable of forming a resist pattern with excellent resolution and adhesion and a reduced amount of resist fringing with excellent sensitivity, a photosensitive element using the same, a method of forming a resist pattern, and a method of manufacturing a printed wiring board are provided. can be provided.

[Figure 1] A schematic cross-sectional view showing one embodiment of the photosensitive element of the present disclosure.
[Figure 2] A perspective view schematically showing an example of the manufacturing process of a printed wiring board using a semi-additive method.

Hereinafter, modes for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In addition, in this specification, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylate means acrylate or methacrylate. The (poly)oxyethylene group means at least one type of an oxyethylene group (sometimes referred to as an "EO group") or a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The (poly)oxypropylene group means at least one type of an oxypropylene group (sometimes referred to as a "PO group") or a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. In addition, "EO modified" means a compound having a (poly)oxyethylene group, "PO modified" means a compound having a (poly)oxypropylene group, and "EO·PO modified" means a compound having a (poly)oxypropylene group. It means a compound having both an oxyethylene group and a (poly)oxypropylene group.

In addition, in this specification, the term "process" is included in this term not only as an independent process, but also in cases where the process cannot be clearly distinguished from other processes as long as the desired effect of the process is achieved. In addition, in this specification, the numerical range indicated using "~" represents a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. In addition, in the numerical range described in stages in this specification, the upper or lower limit of the numerical range at a certain level may be replaced with the upper or lower limit of the numerical range at another level. In addition, in the numerical range described in this specification, the upper or lower limit of the numerical range may be replaced with the value shown in the examples. In addition, in this specification, the term "layer" includes structures formed on a part of the layer in addition to structures formed on the entire surface when viewed from a planar view.

In addition, in this specification, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component exist in the composition.

<Photosensitive resin composition>

The photosensitive resin composition of this embodiment consists of (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: 2,4,5-triarylimidazole dimer and its derivatives. A photopolymerization initiator containing at least one selected from the group consisting of a component (D): a nitroxyl compound, wherein the component (D) is 2,2,6,6-tetramethylpiperidine-1-oxyl Includes compounds with a structure. The photosensitive resin composition may further contain other components as needed. In addition, in this specification, these components may simply be referred to as (A) component, (B) component, (C) component, (D) component, etc.

A binder polymer, a photopolymerizable compound, a photopolymerization initiator containing at least one member selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives, and 2,2,6,6-tetra By using a photosensitive resin composition containing a nitroxyl compound containing a compound having a methylpiperidine-1-oxyl structure, the resolution of L/S (line width/space width) is 10/10 (unit: ㎛) or less. and adhesion, and a resist pattern with a reduced amount of resist hem generation can be formed with excellent sensitivity. Here, it is presumed that the reason why excellent adhesion can be obtained and the amount of resist hem generation is reduced is because by using the photosensitive resin composition, the curing rate at the bottom of the resist pattern is improved and swelling of the resist pattern is suppressed.

((A) Ingredient: Binder polymer)

(A) Components include, for example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and epoxy obtained by reaction of epoxy resin and (meth)acrylic acid. Acrylate resin, acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin and acid anhydride, etc. are mentioned. These resins can be used individually or in combination of two or more types. From the viewpoint of superior alkaline developability and film formation, it is preferable to use an acrylic resin, and among the acrylic resins, a structural unit derived from (a1) (meth)acrylic acid (hereinafter also referred to as (a1) component), and It is more preferable to use an acrylic resin containing a structural unit derived from (a2) (meth)acrylic acid alkyl ester (hereinafter also referred to as (a2) component). Here, “acrylic resin” means a polymer mainly having monomer units derived from a polymerizable monomer having a (meth)acrylic group.

The acrylic resin is, for example, a polymerizable monomer (monomer) that contains (meth)acrylic acid, (meth)acrylic acid alkyl ester, and other polymerizable monomers used as necessary, by a conventional method, It can be obtained by polymerization.

(a1) The content of structural units derived from (meth)acrylic acid is based on the total mass of structural units derived from the polymerizable monomers constituting the binder polymer (100 mass) from the viewpoint of more effectively demonstrating developability and peeling properties. %, the same applies hereinafter), it may be 1 to 99 mass%, 5 to 80 mass%, 10 to 60 mass%, or 15 to 50 mass%.

(a2) As the (meth)acrylic acid alkyl ester, (meth)acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferable, and (meth)acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is more preferable. Examples of alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylate. ) Heptyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. These can be used individually or in any combination of two or more types.

(a2) The content of the structural unit derived from the (meth)acrylic acid alkyl ester is based on the total mass (100% by mass) of the structural unit derived from the polymerizable monomer constituting the binder polymer in terms of superior peelability. It may be 1 mass% or more, or 2 mass% or more. In addition, for superior resolution and adhesion, this content may be 30% by mass or less, 20% by mass or less, or 10% by mass or less.

The acrylic resin may further contain other monomers that can copolymerize with the component (a1) and/or component (a2) as structural units.

There are no particular restrictions on other monomers that can be copolymerized with the above-mentioned component (a1) and/or component (a2). Examples of the other monomers include benzyl (meth)acrylate, cycloalkyl (meth)acrylate, benzyl (meth)acrylate derivative, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylate. Isobornyl acrylate, adamantyl (meth)acrylate, dicyclofentanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2, 2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate , isobornyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, adamantyloxyethyl (meth)acrylate, dicyclopentenyloxypropyloxyethyl (meth)acrylate, dicyclofentanyl (meth)acrylate (meth)acrylic acid esters such as oxypropyloxyethyl, dicyclopentenyloxypropyloxyethyl (meth)acrylate, and adamantyloxypropyloxyethyl (meth)acrylate; (meth)acrylic acid derivatives such as α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, and β-styryl (meth)acrylic acid; Polymerizable styrene derivatives substituted at the α-position or aromatic ring, such as styrene, vinyl toluene, and α-methylstyrene; Acrylamides such as diacetone acrylamide; acrylonitrile; Ether compounds of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; Maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; Unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid; etc. can be mentioned. These can be used individually or in combination of two or more types.

In addition, the acrylic resin may further have a structural unit derived from styrene or a derivative thereof, or a structural unit derived from benzyl (meth)acrylate, from the viewpoint of further reducing the resist hem. From the viewpoint of improving resolution, it may further have a structural unit derived from benzyl (meth)acrylate.

The content of structural units derived from benzyl (meth)acrylate in the above-mentioned acrylic resin is based on the total mass of structural units derived from polymerizable monomers constituting the binder polymer (100% by mass, or less) in that the resolution is superior. (same), it may be 3% by mass or more, 5% by mass or more, or 10% by mass or more. In addition, in terms of superior peelability and adhesion, this content may be 85 mass% or less, 75 mass% or less, 70 mass% or less, or 50 mass% or less.

The acid value of component (A) may be 90 mgKOH/g or more, 100 mgKOH/g or more, 120 mgKOH/g or more, or 130 mgKOH/g or more in order to further shorten the development time. In addition, in order to further improve the adhesion of the cured product of the photosensitive resin composition, the acid value may be 250 mgKOH/g or less, 240 mgKOH/g or less, 235 mgKOH/g or less, or 230 mgKOH/g or less.

(A) The acid value of component can be measured as follows. That is, first, 1 g of the binder polymer, which is the object of acid value measurement, is accurately weighed. 30 g of acetone is added to the accurately weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein, an indicator, is added to the solution, and titration is performed using a 0.1N aqueous potassium hydroxide (KOH) solution. The acid value is determined by calculating the mg number of KOH required to neutralize the acetone solution of the binder polymer to be measured. When measuring a solution in which a binder polymer is mixed with a synthetic solvent, diluting solvent, etc., the acid value is calculated using the following equation.

Acid value=0.1×Vf×56.1/(Wp×I/100)

In the formula, Vf represents the appropriate amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the solution containing the measured binder polymer, and I represents the ratio of non-volatile matter in the solution containing the measured binder polymer (mass %).

Additionally, when blending the binder polymer in a mixed state with volatile components such as a synthetic solvent or diluting solvent, it is heated in advance at a temperature 10°C or more higher than the boiling point of the volatile component for 1 to 4 hours before weighing, and the volatile component is removed and then the acid value is adjusted. can also be measured.

When the weight average molecular weight (Mw) of component (A) is measured by gel permeation chromatography (GPC) (converted using a calibration curve using standard polystyrene), in terms of superior developability, it is 200,000 or less, 100,000 or less, It may be 80000 or less, or 60000 or less. For superior adhesion, this weight average molecular weight may be 10,000 or more, 15,000 or more, 20,000 or more, or 23,000 or more.

The dispersion degree (weight average molecular weight/number average molecular weight) of component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of superior resolution and adhesion.

Component (A) may, if necessary, have a characteristic group in its molecule that is photosensitive to light having a wavelength within the range of 340 nm to 430 nm. The characteristic group includes a group formed by removing at least one hydrogen atom from a sensitizer described later.

In terms of further improving the formability of the film (photosensitive resin composition layer), the content of component (A) is 30 parts by mass or more, 35 parts by mass or more, in 100 parts by mass of the total amount of component (A) and component (B). , or it may be 40 parts by mass or more. In addition, in order to further improve sensitivity and resolution, this content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

((B) Ingredient: Photopolymerizable compound)

(B) As the component, a photopolymerizable compound having an ethylenically unsaturated group can be used.

Examples of the compound having an ethylenically unsaturated group include compounds having one ethylenically unsaturated group in the molecule, compounds having two ethylenically unsaturated groups in the molecule, and compounds having three or more ethylenically unsaturated groups in the molecule.

The component (B) preferably contains at least one compound having two ethylenically unsaturated groups in the molecule. When a compound having two ethylenically unsaturated groups is included in the molecule, its content is 5 parts by mass to 70 parts by mass, or 5 parts by mass to 65 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B). , or it may be 10 parts by mass to 60 parts by mass.

Examples of compounds having two ethylenically unsaturated groups in the molecule include bisphenol-type di(meth)acrylate, hydrogenated bisphenol A-based di(meth)acrylate, di(meth)acrylate having a urethane bond in the molecule, and EO. ·PO modified polyalkylene glycol di(meth)acrylate, trimethylol propane di(meth)acrylate, etc. are mentioned.

From the viewpoint of further improving resolution and peeling properties, the component (B) includes bisphenol-type di(meth)acrylate, hydrogenated bisphenol A-based di(meth)acrylate, and EO·PO-modified polyalkylene glycol di(meth)acrylate. It is preferable to contain at least one type of compound having two ethylenically unsaturated groups in the molecule selected from the group consisting of acrylates, and more preferably to contain at least one type of bisphenol type di(meth)acrylate compound, EO It is more preferable to include at least one type of bisphenol-type di(meth)acrylate compound having a group.

As the bisphenol type di(meth)acrylate, a compound represented by the following general formula (4) can be used.

In the general formula (4), R ² and R ³ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an EO group or a PO group. (XO) _r1 , (XO) _r2 , (YO) _s1 , and (YO) _s2 each represent a (poly)oxyethylene group or a (poly)oxypropylene group. r1, r2, s1 and s2 each independently represent 0 to 40. r1, r2, s1 and s2 represent the number of structural units of the structural unit. Therefore, for a single molecule, it represents an integer value, and for a collection of multiple types of molecules, it represents a rational number that is the average value. Hereinafter, the number of structural units is the same.

When the compound represented by the general formula (4) has a PO group, the total number of structural units of the PO group in the compound may be 2 or more, or 3 or more, because the register resolution is superior. Additionally, from the viewpoint of superior developability, the total number of structural units of the PO group may be 5 or less.

When the compound represented by the general formula (4) has an EO group, the total number of structural units of the EO group in the compound may be 4 or more, 6 or more, or 8 or more because of superior developability. . Additionally, from the viewpoint of better resolution, the total number of structural units of the EO group may be 16 or less, or 14 or less.

Among the compounds represented by the general formula (4), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane is FA-3200MY (Hitachi Kasei Co., Ltd.), 2 , 2-bis(4-(methacryloxydiethoxy)phenyl)propane is commercially available as FA-324M (Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxypenta) Ethoxy) phenyl) propane is commercially available as BPE-500 (Shin Nakamura Chemical Co., Ltd.) or FA-321M (Hitachi Chemical Co., Ltd.), and is 2,2-bis (4- (meta) Kryloxypentadecaethoxy)phenyl)propane is commercially available as BPE-1300 (Shin Nakamura Chemical Co., Ltd.). These are used individually or in arbitrary combination of two or more types.

When the photosensitive resin composition contains bisphenol-type di(meth)acrylate, its content is 1 to 65 parts by mass, 5 to 60 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B), Alternatively, it may be 10 to 55 parts by mass.

Examples of hydrogenated bisphenol A di(meth)acrylates include 2,2-bis(4-(methacryloxypentaethoxy)cyclohexyl)propane. When the photosensitive resin composition contains hydrogenated bisphenol A di(meth)acrylate, its content is 1 to 50 parts by mass, or 5 parts by mass, in 100 parts by mass of the total amount of component (A) and component (B). It may be ~40 parts by mass.

In EO·PO modified polyalkylene glycol di(meth)acrylate, the (poly)oxyethylene group and (poly)oxypropylene group within the molecule may exist continuously in blocks or may exist randomly. do. Additionally, in the (poly)oxyisopropylene group, the secondary carbon of the isopropylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

Commercially available as EO·PO modified polyalkylene glycol di(meth)acrylate, for example, polyalkylene glycol di(meth) having EO group: 6 (average value) and PO group: 12 (average value) ) Acrylate (Hitachi Kasei Co., Ltd., "FA-023M"), polyalkylene glycol di(meth)acrylate (Hitachi Kasei Co., Ltd.) with EO group: 6 (average value) and PO group: 12 (average value) Note), “FA-024M”), etc.

When the photosensitive resin composition contains EO·PO modified polyalkylene glycol di(meth)acrylate, its content is from the viewpoint of improving resolution in 100 parts by mass of the total amount of component (A) and component (B). , it may be 5 to 30 parts by mass, or 10 to 20 parts by mass.

The component (B) may contain at least one photopolymerizable compound having three or more ethylenically unsaturated groups in the molecule.

Compounds having three or more ethylenically unsaturated groups include, for example, trimethylolpropane tri(meth)acrylate and EO-modified trimethylolpropane tri(meth)acrylate (the number of structural units of the oxyethylene group is 1 to 5). , PO modified trimethylolpropane tri(meth)acrylate, EO·PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate, penta Examples include erythritol tri(meth)acrylate, EO-modified pentaerythritol tetraacrylate, or dipentaerythritol hexa(meth)acrylate. These can be used individually or in combination of two or more types.

Tetramethylolmethane triacrylate is A-TMM-3 (Shin Nakamura Chemical Co., Ltd.), and EO-modified trimethylolpropane trimethacrylate is TMPT21E and TMPT30E (Hitachi Chemical Co., Ltd.). Pentaerythritol triacrylate is SR444 (Certomer Co., Ltd.), and dipentaerythritol hexaacrylate is A-DPH (Shinnakamura Chemical Co., Ltd.), which is EO-modified pentaerythritol tetraacrylate. is commercially available as ATM-35E (Shin Nakamura Chemical Co., Ltd.).

When a photopolymerizable compound having three or more ethylenically unsaturated groups is included in the molecule, the content thereof is based on component (A) and (B) from the viewpoint of further improving the resolution, adhesion, resist shape, and peeling properties after curing in a balanced manner. ) It may be 3 to 30 parts by mass, 5 to 25 parts by mass, or 5 to 20 parts by mass out of 100 parts by mass of the total amount of components.

The component (B) is a photopolymerizable component having one ethylenically unsaturated group in the molecule, in that it can further improve the resolution, adhesion, resist shape, and peeling properties after curing in a balanced manner, or can further suppress the generation of residues. Compounds may be included.

Examples of photopolymerizable compounds having one ethylenically unsaturated group in the molecule include nonylphenoxypolyoxyethylene acrylate, phthalic acid compounds, and (meth)acrylic acid alkyl esters. Among the above, it is preferable to include nonylphenoxypolyoxyethylene acrylate or a phthalic acid compound from the viewpoint of further improving the resolution, adhesion, resist shape, and peeling characteristics after curing in a balanced manner.

When a photopolymerizable compound having one ethylenically unsaturated group is included in the molecule, the content is 1 to 20 parts by mass, 3 to 15 parts by mass, or , may be 5 to 12 parts by mass.

The content of the entire component (B) in the photosensitive resin composition is 30 to 70 parts by mass, 35 to 65 parts by mass, or 35 to 60 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B). It may be a mass part. When this content is 30 parts by mass or more, sensitivity and resolution tend to further improve. If this content is 70 parts by mass or less, it tends to become easy to form a film (photosensitive resin composition layer) and it also tends to become easy to obtain a good resist shape.

((C)Component: Photopolymerization initiator)

The photosensitive composition contains, as component (C), a photopolymerization initiator containing at least one type selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives. The 2,4,5-triarylimidazole dimer and its derivatives further improve sensitivity and adhesion and further reduce the amount of register fringing, so the compound represented by the general formula (1) is used. You may include it.

In General Formula (1), it is preferable that at least one of X ¹ and X ² is a chlorine atom. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently an aryl group having at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group, the number of the substituents is preferably 1 to 5. It is more preferable that it is 1 to 3, and it is even more preferable that it is 1. Additionally, when Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently an aryl group having the above substituent, the substitution position is not particularly limited, and is preferably the ortho or para position. p and q are each independently an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1.

Compounds represented by the general formula (1) include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5- Di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl Midazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer are included. In addition, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same, and a target compound may be given, or a compound that is mutually asymmetric may be given. These are used individually or in combination of two or more types.

(C) As component, in addition to the said 2,4,5-triarylimidazole dimer or its derivative(s), other commonly used photopolymerization initiators may be contained. Other photopolymerization initiators include, for example, benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (mihyracetone), N,N,N',N' -Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, Octamethylanthraquinone, 1, 2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, Quinones such as 4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, and benzoin. Benzoin ether compounds such as phenyl ether, benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl) oxime), oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), and benzyl such as benzyldimethylketal. Derivatives include acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine, and N-phenylglycine derivatives.

The content of component (C) may be 0.1 to 10 parts by mass, 1 to 7 parts by mass, 2 to 6 parts by mass, or 3 to 5 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). do. When the content of component (C) is 0.1 parts by mass or more, it becomes easier to obtain better sensitivity, resolution, or adhesion, and at the same time, there is a tendency to further reduce the amount of resist hem generation, and when it is 10 parts by mass or less, a better resist shape is achieved. tends to become easier to obtain.

((D) Ingredient: Nitroxyl compound)

A nitroxyl compound means a compound having a nitroxyl group. A nitroxyl group can also be said to be a group represented by the following structural formula (5).

(D) Component is a nitroxyl compound and includes a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure. By using the compound having the above structure in combination with at least one member selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives, resolution and adhesion are excellent, and the amount of register fringing is reduced. A photosensitive resin composition capable of forming a resist pattern with excellent sensitivity can be obtained.

The compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure may be a compound represented by the following general formula (2). When the photosensitive resin composition contains a compound represented by the following general formula (2), the resolution and adhesion of the formed resist pattern can be further improved while having good sensitivity, and the amount of resist fringing can be further reduced. .

[In formula (2), R ¹ represents a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, an acetamide group, an amino group, a chloroacetamide group, a cyano group, a benzoyloxy group, or a group represented by the following general formula (3) .]

[In formula (3), n1 represents an integer of 1 to 12.]

In addition, in the photosensitive resin composition, the compound represented by the general formula (2) may exist in a state where the free radical moiety is bonded to another compound or organic group, etc.

In General Formula (2), R ¹ is preferably a hydroxyl group, an acetamide group, or a benzoyloxy group. If R ¹ is a hydroxyl group, the amount of resist hem generation can be further reduced. If R ¹ is an acetamide group or a benzoyloxy group, sensitivity can be further improved.

Compounds represented by general formula (2) include, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-hydroxy-2,2,6 ,6-tetramethylpiperidine-1-oxylbenzoate free radical, 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-amino-2,2, 6,6-Tetramethylpiperidine-1-oxyl free radical, 4-(2-chloroacetamide)-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-cyano 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical. These can be used individually or in any combination of two or more types.

Other compounds having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure include, for example, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical. You can. This compound can be used in combination with the compound represented by general formula (2), but it is difficult to use alone because it is highly volatile.

(D) As the component, you may contain a nitroxyl compound other than a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure.

The content of component (D) may be 0.005 to 10 parts by mass, 0.01 to 8 parts by mass, or 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of component (A). When this content is 0.005 parts by mass or more, resolution and adhesion tend to be more excellent, and when this content is 10 parts by mass or less, sensitivity tends to be more excellent. The content of component (D) may be 0.005 to 20 parts by mass, 0.01 to 5 parts by mass, or 0.02 to 1 part by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). When this content is 0.005 parts by mass or more, resolution and suppression of the amount of register fringing tend to be more excellent, and when this content is 20 parts by mass or less, sensitivity tends to be more excellent.

((E) Ingredient: Phenol-based compound)

It is more preferable that the photosensitive resin composition contains at least one type of phenolic compound in combination with the components (A) to (D) from the viewpoint of further improving resolution. (E) Components include, for example, 2,2-methylene-bis(4-methyl-6-tertiary butylphenol), catechol, picric acid, 4-tertiary-butylcatechol, and 2,6-tertiary. butyl-p-cresol, 4,4'-thiobis[ethylene(oxy)(carbonyl)(ethylene)]bis[2,6-bis(1,1-dimethylethyl)phenol], etc.

The content of component (E) may be 0.0001 to 1 part by mass, 0.001 to 0.1 part by mass, or 0.005 to 0.01 part by mass with respect to 100 parts by mass of the total amount of component (A). When this content is 0.0001 parts by mass or more, resolution and adhesion tend to be more excellent, and when it is 1 part by mass or less, sensitivity tends to be more excellent.

In addition to the above-mentioned (A) to (E) components, the photosensitive resin composition of one embodiment of the present disclosure preferably contains (F) component: sensitizer and/or (G) component: hydrogen donor.

((F) Ingredient: Sensitizer)

It is preferable that the photosensitive resin composition contains at least one type of sensitizer. The sensitizer is one that can effectively utilize the absorption wavelength of the actinic light used for exposure, and a compound with a maximum absorption wavelength of 340 nm to 420 nm is preferable.

(F) Components include, for example, pyrazoline compounds, anthracene compounds, acridone compounds, coumarin compounds, xanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds. , stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, etc. In particular, from the viewpoint of further improving resolution, adhesion, and sensitivity, component (F) preferably contains a pyrazoline compound or an anthracene compound, and more preferably contains a pyrazoline compound. (F) The sensitizer which is a component can be used individually by one type or in combination of two or more types.

The pyrazoline compound may be a compound represented by the following general formula (6) from the viewpoint of improving sensitivity and resolution in a balanced manner.

In general formula (6), R represents an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 12 carbon atoms, a, b and c each independently represent an integer of 0 to 5, and the total of a, b and c is 1 to 6. When the total of a, b and c is 2 to 6, plural R in the same molecule may be the same or different.

Said R may be linear or branched. Examples of R include, but are not limited to, methoxy group, isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, and dodecyl group. In addition, the total of a, b and c in general formula (6) is 1 to 6, but it is more preferable that it is 1 to 4, and it is especially preferable that it is 1 or 2.

From the viewpoint of further improving sensitivity and solubility, the compound represented by the general formula (6) is preferably a pyrazoline compound where R is an alkoxy group with 1 to 10 carbon atoms or an alkyl group with 1 to 3 carbon atoms. Among them, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline is particularly preferred from the viewpoint of improving ease of synthesis and sensitivity, and ease of synthesis and solvent From the viewpoint of improving solubility, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)pyrazoline is particularly preferred.

When the photosensitive resin composition contains a pyrazoline compound as component (F), 2,4,5-triarylimidazole dimer or a derivative thereof and 2,2,6,6-tetramethylpiperidine-1-oxyl By combining it with a compound having a structure, the effect of improving sensitivity, resolution, and adhesion, and the effect of reducing the amount of register fringing can be further enhanced. That is, 3 components: 2,4,5-triarylimidazole dimer or a derivative thereof, a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure, and a pyrazoline compound. By the combination, very good sensitivity, resolution, and adhesion can be obtained, and the amount of register hem generation can be significantly reduced.

When the photosensitive resin composition contains component (F), the content is 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 100 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B). It may be 3 parts by mass. If this content is 0.01 parts by mass or more, sensitivity and resolution tend to be superior and the amount of resist fringing can be further reduced, and if this content is 10 parts by mass or less, it tends to become easier to obtain a better resist shape.

((G)Component: Hydrogen donor)

The photosensitive resin composition may contain at least one type of hydrogen donor from the viewpoint of improving the contrast (also referred to as “imagingability”) between the exposed portion and the unexposed portion. The hydrogen donor is not particularly limited as long as it can provide hydrogen to the photopolymerization initiator during reaction in the exposed area, for example, bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl. ]Methane, Royco Crystal Violet, etc. can be mentioned. These can be used individually or in combination of two or more types.

When component (G) is included, the content may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 2 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B). do. When this content is 0.01 mass part or more, it tends to become easier to obtain better sensitivity. If this content is 10 parts by mass or less, precipitation of excess (G) component as a foreign matter after film formation tends to be suppressed.

(Other ingredients)

The photosensitive resin composition of the present embodiment may optionally contain a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, Victoria pure blue, brilliant green. , dyes such as methyl violet, photochromic agents such as tribromophenyl sulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, 2-chloroaniline, thermochromic inhibitors, plasticizers such as 4-toluenesulfone amide, It may contain pigments, fillers, anti-foaming agents, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, heat cross-linking agents, etc. These are used individually or in combination of two or more types. When the photosensitive resin composition contains other components, it is preferable that their content is about 0.01 to 20 parts by mass, respectively, with respect to 100 parts by mass of the total amount of component (A) and component (B).

[Solution of photosensitive resin composition]

The photosensitive resin composition of this embodiment may further contain at least 1 type of organic solvent in order to adjust the viscosity as needed. Examples of organic solvents include alcohol solvents such as methanol and ethanol; Ketone solvents such as acetone and methyl ethyl ketone; Glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; Aromatic hydrocarbon solvents such as toluene; Aprotic polar solvents such as N,N-dimethylformamide, etc. can be mentioned. These may be used individually or in combination of two or more types. The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose, etc. For example, the photosensitive resin composition can be used as a solution with a solid content of about 30 to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid.”

A photosensitive resin composition layer can be formed using the photosensitive resin composition by applying (for example, applying) the above-mentioned coating liquid to the surface of a support, a metal plate, etc., which will be described later, and drying it. The metal plate is not particularly limited and can be appropriately selected depending on the purpose, etc. Examples of the metal plate include metal plates such as copper, copper-containing alloys, nickel, chromium, iron, and iron-containing alloys such as stainless steel. As the metal plate, metal plates such as copper, copper-containing alloy, and iron-containing alloy are preferably used.

The thickness of the formed photosensitive resin composition layer is not particularly limited and can be appropriately selected depending on the intended use. The thickness of the photosensitive resin composition layer may be, for example, 1 to 100 μm after drying. When the photosensitive resin composition layer is formed on a metal plate, the surface of the photosensitive resin composition layer on the opposite side to the metal plate may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

The photosensitive resin composition can be applied to the formation of the photosensitive resin composition layer of the photosensitive element described later. That is, another embodiment of the present disclosure includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: 2,4,5-triarylimidazole dimer and the same. It contains a photopolymerization initiator containing at least one type selected from the group consisting of derivatives, and (D) component: a nitroxyl compound, wherein the (D) component is 2,2,6,6-tetramethylpiperidine-1. -It is an application to a photosensitive element of a photosensitive resin composition containing a compound having an oxyl structure.

In addition, the photosensitive resin composition of this embodiment can be used in the resist pattern formation method described later. That is, another embodiment of the present disclosure includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: 2,4,5-triarylimidazole dimer and the same. It contains a photopolymerization initiator containing at least one type selected from the group consisting of derivatives, and (D) component: a nitroxyl compound, wherein the (D) component is 2,2,6,6-tetramethylpiperidine-1. -It is an application to a method of forming a resist pattern of a photosensitive resin composition containing a compound having an oxyl structure.

＜Photosensitive element＞

The photosensitive element of one embodiment of the present disclosure includes a support and a photosensitive resin composition layer formed from the photosensitive resin composition provided on the support. Additionally, the photosensitive resin composition layer may be a coating film. The coating film referred to in this specification refers to the photosensitive resin composition in an uncured state. The photosensitive element may have other layers, such as a protective layer, as needed.

Figure 1 shows one embodiment of a photosensitive element. In the photosensitive element 1 shown in FIG. 1, the support 2, the photosensitive resin composition layer 3 formed of the photosensitive resin composition, and the protective layer 4 are laminated in this order. The photosensitive element 1 can be obtained, for example, as follows. A coating liquid (i.e., a photosensitive resin composition containing an organic solvent) is applied on the support 2 to form a coating layer, and then dried to form the photosensitive resin composition layer 3. Next, the surface of the photosensitive resin composition layer 3 opposite to the support 2 is covered with the protective layer 4, thereby forming the support 2 and the photosensitive resin composition layer 3 formed on the support 2. and a protective layer (4) laminated on the photosensitive resin composition layer (3). The photosensitive element (1) of this embodiment can be obtained. The photosensitive element 1 does not necessarily need to be provided with the protective layer 4.

As the support, a polymer film made of a polymer having heat resistance and solvent resistance, such as polyester such as polyethylene terephthalate, or polyolefin such as polypropylene or polyethylene, can be used.

The thickness of the support (polymer film) may be 1 to 100 μm, 5 to 50 μm, or 5 to 30 μm. When the thickness of the support is 1 μm or more, tearing of the support can be prevented when peeling off the support. In addition, a decrease in resolution is suppressed by being 100 μm or less.

As a protective layer, it is preferable that the adhesive force to the photosensitive resin composition layer is smaller than the adhesive force to the photosensitive resin composition layer of the support. Additionally, a low fish eye film is preferred. Here, “fish eye” refers to the fact that when a material is heat-melted and a film is manufactured by kneading, extrusion, biaxial stretching, casting, etc., foreign substances, undissolved substances, oxidation deteriorated substances, etc. of the material are present in the film. It means taken in. In other words, “low fish eye” means that there is little foreign matter in the film.

Specifically, as the protective layer, a polymer film made of a polymer having heat resistance and solvent resistance, such as polyester such as polyethylene terephthalate or polyolefin such as polypropylene and polyethylene, can be used. Commercially available products include Alpan MA-410 and E-200 from Oji Seishi Co., Ltd., polypropylene films from Shin-Etsu Film Co., Ltd., and PS-series polyethylene terephthalate films such as Teijin Co., Ltd.'s PS-25. I can hear it. Additionally, the protective layer 4 may be the same as the support 2.

The thickness of the protective layer may be 1 to 100 μm, 5 to 50 μm, 5 to 30 μm, or 15 to 30 μm. If the thickness of the protective layer is 1 μm or more, tearing of the protective layer can be prevented when the photosensitive resin composition layer and the support are laminated on the substrate while peeling off the protective layer. If the thickness of the protective layer is 100 μm or less, handling and low cost are excellent.

The photosensitive element of this embodiment can be specifically manufactured as follows, for example. (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: at least one member selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof. A step of preparing a coating solution containing a photopolymerization initiator and (D) component: a nitroxyl compound containing a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure dissolved in an organic solvent; , It can be manufactured by a manufacturing method that includes a step of forming an application layer by applying (for example, applying) the coating liquid on a support, and a step of drying the application layer to form a photosensitive resin composition layer.

The application of the solution of the photosensitive resin composition onto the support can be performed by known methods such as roll coat, comma coat, gravure coat, air knife coat, die coat, and bar coat.

Drying of the application layer is not particularly limited as long as at least part of the organic solvent can be removed from the application layer, and can be dried at, for example, 70 to 150°C for 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin composition layer may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in subsequent processes.

The thickness of the photosensitive resin composition layer in the photosensitive element can be appropriately selected depending on the intended use. The thickness of the photosensitive resin composition layer may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm after drying. When the thickness of the photosensitive resin composition layer is 1 μm or more, industrial coating becomes easy. When it is 100 μm or less, adhesion and resolution tend to be more excellent.

The transmittance of the photosensitive resin composition layer to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% for ultraviolet rays in the wavelength range of 350 nm to 420 nm. When this transmittance is 5% or more, it tends to become easier to obtain better adhesion. If it is 75% or less, it tends to become easier to obtain better resolution. Additionally, transmittance can be measured using a UV spectrometer. As a UV spectrometer, a 228A type W-beam spectrophotometer manufactured by Hitachi Seisakusho Co., Ltd. can be used.

The photosensitive element may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, for example, the intermediate layer described in Japanese Patent Application Laid-Open No. 2006-098982 can be applied also in one embodiment of the present disclosure.

The photosensitive element of this embodiment can be suitably used, for example, in the resist pattern formation method described later.

＜Method of forming a resist pattern＞

A resist pattern can be formed using the photosensitive resin composition or the photosensitive element. The method of forming a resist pattern of this embodiment includes (i) a step of forming a photosensitive resin composition layer on a substrate using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step), and (ii) the photosensitive layer forming step. A step (exposure step) of irradiating actinic light to at least a portion of the resin composition layer to photocure the region to form a cured region, (iii) a region other than the cured region of the photosensitive resin composition layer; There is a process (development process) of removing from the substrate to form a resist pattern, which is the cured product area, on the substrate. The resist pattern forming method may further include other steps as needed, and the photosensitive resin composition layer in the photosensitive layer forming step may be a coating film. In addition, the photosensitive resin composition and the photosensitive element can also be applied to a method of manufacturing a substrate with a resist pattern, in which a substrate with a resist pattern is obtained by the method of forming the resist pattern.

(i) Photosensitive layer formation process

First, a photosensitive resin composition layer is formed on a substrate using the photosensitive resin composition or the photosensitive element. As the substrate, a substrate (substrate for circuit formation) provided with an insulating layer and a conductor layer formed on the insulating layer can be used.

Formation of the photosensitive resin composition layer on the substrate may be performed, for example, when the photosensitive element has a protective layer 4, by removing the protective layer and then pressing the photosensitive resin composition layer of the photosensitive element onto the substrate while heating. It is carried out by doing. When using a photosensitive resin composition, the photosensitive resin composition layer can be formed by applying (for example, applying) the coating liquid to the surface of the substrate and drying it. In this way, a laminate in which the substrate, the photosensitive resin composition layer, and the support are laminated in this order can be obtained.

This photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating of at least one of the photosensitive resin composition layer and the substrate during compression is preferably performed at a temperature of 70 to 130°C, and compression is performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). desirable. These conditions are not particularly limited and are appropriately selected according to need. Additionally, if the photosensitive resin composition layer is heated to 70 to 130°C, there is no need to preheat the substrate in advance. Adhesion and followability can be further improved by preheating the substrate for circuit formation.

(ii) Exposure process

In the exposure process, actinic light is irradiated to at least a portion of the photosensitive resin composition layer formed on the substrate as described above, so that the exposed portion irradiated with actinic light is photocured, thereby forming a latent image. At this time, when a support exists on the photosensitive resin composition layer, if the support is transparent to actinic light, actinic light can be irradiated through the support. On the other hand, when the support exhibits light-shielding properties against actinic rays, actinic rays are irradiated to the photosensitive resin composition layer after the support is removed.

Examples of the exposure method include a method (mask exposure method) of irradiating actinic light onto an image through a negative or positive mask pattern called artwork. Additionally, a method of irradiating actinic light onto an image by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be adopted.

The light source of actinic light is not particularly limited, and a known light source can be used. For example, ultraviolet rays such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, semiconductor lasers, and blue-purple lasers such as gallium nitride, etc. One that effectively radiates visible light or the like is used.

The wavelength (exposure wavelength) of the actinic light is preferably within the range of 340 to 430 nm, and more preferably within the range of 350 to 420 nm, from the viewpoint of more reliably obtaining the effect of one embodiment of the present disclosure.

(iii) Development process

In the development process, the uncured portion of the photosensitive resin composition layer is removed from the circuit forming substrate by developing treatment, thereby forming a resist pattern in which the photosensitive resin composition layer is a photocured cured product on the substrate. When a support is present on the photosensitive resin composition layer, the support is removed, and then the unexposed portion is removed (developed). There are two types of development treatment: wet development and dry development, but wet development is widely used.

In the case of wet development, development is performed by a known developing method using a developing solution corresponding to the photosensitive resin composition. Development methods include methods using a dip method, paddle method, spray method, brushing, slapping, scrubbing, oscillation immersion, etc., and from the viewpoint of improving resolution, a high-pressure spray method is preferable. Development may be performed by combining two or more of these methods.

The developing solution is appropriately selected depending on the structure of the photosensitive resin composition. Examples of developing solutions include alkaline aqueous solutions and organic solvent developing solutions.

When an alkaline aqueous solution is used as a developer, it is safe and stable and has good operability. Examples of the base in the alkaline aqueous solution include alkali hydroxides such as hydroxide of lithium, sodium, or potassium; Alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; Alkali metal phosphates such as potassium phosphate and sodium phosphate; Alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, others, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2- Hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine, etc. are used.

The alkaline aqueous solution used for development includes a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, and a diluted solution of 0.1 to 5% by mass of sodium tetraborate. A solution or the like is preferable. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. Additionally, the temperature is adjusted according to the alkaline developability of the photosensitive resin composition layer. The alkaline aqueous solution may contain a small amount of a surface active agent, an antifoaming agent, or a small amount of an organic solvent to promote development.

The alkaline aqueous solution may contain one or more organic solvents. Organic solvents used include acetone, ethyl acetate, alkoxyethanol having an alkoxy group of 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene. Glycol monobutyl ether, etc. can be mentioned. These are used individually or in combination of two or more types. When an organic solvent is included, the content of the organic solvent is preferably 2 to 90% by mass based on the total mass of the alkaline aqueous solution (100% by mass). Additionally, the temperature can be adjusted according to alkali developability. A small amount of surfactant, antifoaming agent, etc. may be mixed into the alkaline aqueous solution used for development.

Organic solvents used in the developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, etc. can be mentioned. To prevent ignition, it is preferable to add water in the range of 1 to 20% by mass to such an organic solvent to prepare an organic solvent developer.

The method of forming a resist pattern further includes a step of removing unexposed portions and then further curing the resist pattern by heating at 60 to 250° C. or exposing to an energy amount of 0.2 to 10 J/cm ² as necessary. You can do it.

＜Manufacturing method of printed wiring board＞

A method of manufacturing a printed wiring board according to an embodiment of the present disclosure includes the method of forming the resist pattern on the conductor layer of a substrate (circuit formation substrate) including an insulating layer and a conductor layer formed on the insulating layer. It includes a process of etching or plating a substrate on which a resist pattern is formed to form a conductor pattern (which may also be referred to as a “circuit pattern”). The manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. The etching process or plating process of the substrate is performed on the conductor layer of the substrate, etc., using the formed resist pattern as a mask.

In the etching process, the resist pattern (cured resist) formed on the substrate is used as a mask, and the conductor layer of the circuit formation substrate that is not covered with the cured resist is etched away to form a conductor pattern. The method of etching treatment is appropriately selected depending on the conductor layer to be removed. Examples of the etching solution include an aqueous cupric chloride solution, an aqueous ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide etching solution. Among these, since it has a good etch factor, an aqueous solution of ferric chloride may be used.

On the other hand, in the plating process, copper, solder, etc. are plated on the conductor layer of the circuit formation substrate that is not covered with the cured resist, using the resist pattern (cured resist) formed on the substrate as a mask. After the plating treatment, the cured resist is removed, and the conductor layer covered by the cured resist is etched to form a conductor pattern. The method of plating may be electrolytic plating or electroless plating. Plating treatments include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-slow solder plating, Watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. and gold plating such as soft gold plating.

After etching and plating, the resist pattern on the substrate is removed (peeled). Removal of the resist pattern can be performed, for example, using an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development process. As this strongly alkaline aqueous solution, a 1-10 mass% aqueous solution of sodium hydroxide, a 1-10 mass% aqueous potassium hydroxide solution, etc. are used. Among them, it is preferable to use 1 to 10 mass% sodium hydroxide aqueous solution or 1 to 10 mass% potassium hydroxide aqueous solution, and it is more preferable to use 1 to 5 mass% sodium hydroxide aqueous solution or 1 to 5 mass% potassium hydroxide aqueous solution. . Methods for applying a strong alkaline aqueous solution to a resist pattern include an immersion method and a spray method, and these may be used individually or in combination of two or more types.

When the resist pattern is removed after plating, the desired printed wiring board can be manufactured by further removing the conductor layer covered with the hardened resist by etching to form a conductor pattern. The method of etching treatment is appropriately selected depending on the conductor layer to be removed. For example, the etching solution described above can be applied.

The method for manufacturing a printed wiring board according to an embodiment of the present disclosure is applicable to the manufacturing of not only a single-layer printed wiring board but also a multi-layer printed wiring board, and is also applicable to the manufacturing of a printed wiring board having a small-diameter through hole, etc. possible.

The photosensitive resin composition of this embodiment can be suitably used in the manufacture of a wiring board. That is, one of the preferred embodiments of one embodiment of the present disclosure is (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: 2,4,5-triaryl imide. A photopolymerization initiator containing at least one member selected from the group consisting of sol dimers and derivatives thereof, and component (D): a nitroxyl compound, wherein component (D) is 2,2,6,6-tetramethyl. Application of a photosensitive resin composition containing a compound having a piperidine-1-oxyl structure to the production of printed wiring boards.

In addition, a more suitable embodiment is the application of the photosensitive resin composition to the production of high-density package substrates, and the application of the photosensitive resin composition to the semi-additive construction method. Below, an example of a wiring board manufacturing process using a semi-additive method will be described with reference to the drawings.

In Figure 2 (a), a substrate (substrate for circuit formation) on which a conductor layer 10 is formed on an insulating layer 15 is prepared. The conductor layer 10 is, for example, a metallic copper layer. In Fig. 2(b), the photosensitive resin composition layer 32 is formed on the conductor layer 10 of the substrate through the photosensitive layer forming process. In Figure 2 (c), the mask 20 is disposed on the photosensitive resin composition layer 32, and through the above exposure process, actinic light 50 is irradiated to the photosensitive resin composition layer 32, and the mask 20 ) is exposed to light to form a photocured portion in the photosensitive resin composition layer 32 . In FIG. 2(d), in the photosensitive resin composition layer 32, regions other than the photocured portion are removed from the substrate through a development process to form a resist pattern 30, which is the photocured portion, on the substrate. In Fig. 2(e), the plating layer 42 is formed on the conductor layer 10 by plating using the resist pattern 30, which is a photocuring portion, as a mask. In Figure 2 (f), after the resist pattern 30, which is a photocured portion, is peeled off with a strong alkali aqueous solution, a part of the plating layer 42 and the conductor layer masked with the resist pattern 30 are subjected to a flash etching process ( 10) is removed to form the conductor pattern 40. The conductor layer 10 and the plating layer 42 may be made of the same or different materials. In FIG. 2 , the method of forming the resist pattern 30 using the mask 20 has been described. However, the resist pattern 30 may be formed by a direct drawing exposure method without using the mask 20.

Example

Hereinafter, an embodiment of the present disclosure will be described in more detail through examples. However, the embodiments of the present disclosure are not limited to the following examples.

(Examples 1 to 11 and Comparative Examples 1 to 7)

(Preparation of solution of photosensitive resin composition)

By mixing the components (A) to (G) and (O) shown in Tables 2 to 4 with 9 g of acetone, 5 g of toluene, and 5 g of methanol in the amount (g unit) shown in the tables, Examples 1 to 11 and Solutions of the photosensitive resin compositions of Comparative Examples 1 to 7 were prepared, respectively. The compounding quantity of (A) component shown in Tables 2 to 4 is the mass (amount of solid content) of non-volatile matter. Details of each component shown in Tables 2 to 4 are as follows. Additionally, “-” means unmixed.

(A) Ingredient: Binder polymer

[Synthesis of binder polymer (A-1)]

Obtained by mixing 90 g of methacrylic acid, 6 g of methyl methacrylate, 150 styrene, and 54 g of benzyl methacrylate (mass ratio 30/2/50/18), which are polymerizable monomers, with 1.5 g of azobisisobutyronitrile. The solution was referred to as “solution a.”

The solution obtained by dissolving 0.5 g of azobis isobutyronitrile in 100 g of a mixed solution of 60 g of methyl cellosolve and 40 g of toluene (mass ratio 3:2) was called “solution b.”

300 g of a mixture of 180 g of methyl cellosolve and 120 g of toluene (mass ratio 3:2) was added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping lot, and nitrogen gas introduction pipe, and nitrogen was added into the flask. Gas was blown in, heated while stirring, and the temperature was raised to 80°C.

The solution a was added dropwise to the mixed solution in the flask at a constant dropping rate over 4 hours, and then stirred at 80°C for 2 hours. Next, the solution b was added dropwise to the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80°C for 3 hours. Additionally, the solution in the flask was heated to 90°C while stirring for 30 minutes, stirred at 90°C for 2 hours, then cooled to room temperature and stirring was stopped to obtain a solution of the binder polymer (A-1). In addition, room temperature as used in this specification means 25°C.

The non-volatile content (solid content) of the binder polymer (A-1) was 47.4 mass%, the weight average molecular weight was 44000, the acid value was 196 mgKOH/g, and the dispersion degree was 1.6.

In addition, the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are shown below.

[GPC conditions]

Pump: Hitachi L-6000 type (Hitachi Seisakusho Co., Ltd.)

Columns: 3 total as shown below, column specifications: 10.7mmϕ×300mm

Gelpack　GL-R440

Gelpack　GL-R450

Gelpack GL-R400M (above, Hitachi Kasei Co., Ltd.)

Eluent: Tetrahydrofuran (THF)

Sample concentration: 120 mg of a binder polymer solution with a non-volatile matter concentration (NV) of 47.4% by mass was collected and dissolved in 5 mL of THF to prepare a sample.

Measurement temperature: 40℃

Injection volume: 200μL

Pressure: 49Kgf/ ^cm2 (4.8MPa)

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 type RI (Hitachi Seisakusho Co., Ltd.)

[Synthesis of binder polymers (A-2) and (A-3)]

Binder polymer (A-2), (A- 3) solution was obtained. The non-volatile content (solid content) of the binder polymers (A-2) and (A-3) was both 47.4% by mass.

Regarding the binder polymers (A-1) to (A-3), Table 1 shows the mass ratio (%), acid value, weight average molecular weight, and dispersion of the polymerizable monomer (monomer). Additionally, “-” means not blended.

(B) Ingredient

B-1: 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (Hitachi Chemical Co., Ltd., “FA-324M”)

B-2: 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (ethylene oxide average 12 mol and propylene oxide adduct average 4 mol) (Hitachi Kasei Co., Ltd.) FA-3200 MY")

B-3: Polyoxyalkylene glycol dimethacrylate (Hitachi Kasei Co., Ltd., "FA-023 M", containing (poly)oxyethylene group (average 6 mol) and (poly)oxypropylene group (average) in the molecule Compound having both sides of 12mol)

(C) Component (2,4,5-triarylimidazole dimer and derivatives thereof)

·C-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole [2-(2-chlorophenyl)-4,5-diphenyl Midazole dimer] (Hampford, “B-CIM”)

(Photopolymerization initiators other than 2,4,5-triarylimidazole dimer and its derivatives)

·C'-2: Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (BASF, "Lucillin TPO")

(D) Ingredient

·D-1: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.)

D-2: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxylbenzoate free radical (Tokyo Kasei Kogyo Co., Ltd.)

·D-3: 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (Tokyo Kasei Kogyo Co., Ltd.)

(E)Ingredients

·E-1: 4-tertiary-butylcatechol (DIC Co., Ltd., “DIC-TBC”)

(F)Ingredients

·F-1: 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline (Nippon Chemical Industries, Ltd.)

F-2: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., “DETX-S”)

・F-3: N-methylacridone (Tokyo Kasei Kogyo Co., Ltd.)

(G)Ingredients

・G-1: Royco Crystal Violet (Yamada Chemical Co., Ltd., “LCV”)

Other ingredients (dye)

・O-1: Marachite Green (Osaka Yugi Chemical Co., Ltd., “MKG”)

＜Production of photosensitive elements＞

The solution of the photosensitive resin composition obtained above was applied onto a polyethylene terephthalate film (Toray Co., Ltd., "FB-40") (support) with a thickness of 16 ㎛, respectively, and dried in a hot air convection dryer at 70°C and 110°C. A drying process was carried out sequentially, and a photosensitive resin composition layer with a dried film thickness of 25 µm was formed. A polypropylene film (Oji Seishi Co., Ltd., "E-200 K") (protective layer) is bonded onto this photosensitive resin composition layer, and the support, the photosensitive resin composition layer, and the protective layer are placed in that order. Each stacked photosensitive element was obtained.

＜Production of laminated boards＞

Copper clad laminate (Hitachi Chemical Co., Ltd., “MCL-E-679F”) consisting of a glass epoxy material and copper foil (thickness 16㎛) formed on both sides (hereinafter referred to as “substrate”) ) was heated to 80°C, and then the photosensitive elements according to Examples 1 to 11 and Comparative Examples 1 to 7 were laminated (stacked) on the copper surface of the substrate. The lamination was performed under the conditions of a temperature of 120°C and a lamination pressure of 4 kgf/cm ² (0.4 MPa) while removing the protective layer and ensuring that the photosensitive resin composition layer of each photosensitive element was in close contact with the copper surface of the substrate. Next, it was left to cool until 23°C, and a laminated substrate was obtained in which the photosensitive resin composition layer and the support were laminated on the copper surface of the substrate.

＜Evaluation of sensitivity＞

On the support of the obtained laminated substrate, a photo tool having a 41-step step tablet with a concentration range of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm × 187 mm, and each step size of 3 mm × 12 mm. was brought into close contact. Using a straight exposure machine (Hitachivia Mechanics Co., Ltd., "DE-1 UH") using a blue-violet laser diode with a wavelength of 405 nm as a light source, the photosensitive resin composition layer is formed through a photo tool and a support. exposed to.

After exposure, the support was peeled from the laminated substrate, the photosensitive resin composition layer was exposed, and an unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution at 30°C for 60 seconds. In this way, a resist pattern made of a cured product of the photosensitive resin composition was formed on the copper surface of the substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the remaining number of steps (number of steps) of the step tablet obtained as a resist pattern (cured film). Sensitivity is expressed by the amount of energy (unit: mJ/cm2) at which the number of steps is 14, and the lower this value, the better the sensitivity. If this value is 200mJ/cm ² or less, it can be said to have sufficient sensitivity. The results are shown in Tables 5 to 7.

＜Evaluation of resolution and adhesion＞

On the support of the obtained laminated substrate, a drawing pattern (resolution) having a line width (L)/space width (S) (hereinafter referred to as "L/S") of 3/3 to 30/30 (unit: ㎛) The drawing pattern for evaluation and the drawing pattern for adhesion evaluation) were brought into close contact. In addition, the drawing pattern for resolution evaluation is a drawing pattern that forms a space (subtraction) in the cured product of the photosensitive resin composition. Next, the photosensitive resin composition layer was exposed (drawn) through the photo tool, drawing pattern, and support using an energy amount such that the remaining stages of the 41-stage step tablet were 14 stages, using the same vertical exposure machine as in the evaluation of sensitivity. . After exposure, the same development process as the above sensitivity evaluation was performed.

After development, the space portion (unexposed portion) is removed and the line portion (exposed portion) is formed by the minimum value of the line width/space width in the resist pattern formed without causing meandering or defects. , resolution (resolution) and adhesion were evaluated. Resolution was evaluated by the minimum value of the space width, and adhesion was evaluated by the minimum value of the line width. The smaller this number, the better both resolution and adhesion. The results are shown in Tables 5 to 7.

＜Field evaluation of register hem＞

In the evaluation of resolution and adhesion, the resist hem (amount of resist hem generated) was evaluated by observing the line portion of the formed resist pattern with a line width of 12 μm. Using a scanning electron microscope (SEM) (Hitachi High Technologies Co., Ltd., "SU-1500"), the resist shape was observed at an acceleration voltage of 15 kV, a magnification of 3,000 times, and a tilt angle of 60 degrees, and the hem of the resist was measured according to the following standards. evaluated. That is, the maximum hem length generated from the side of the register and the bottom of the register was evaluated as “A” if it was 0 μm or more and less than 0.5 μm, and “B” if it was more than 0.5 μm. Additionally, when an undercut was observed at the bottom of the resist, it was evaluated as "C". The evaluation results are shown in Tables 5 to 7.

※1: Evaluation was not possible because a resist pattern with a line width of 12㎛ could not be formed.

As is clear from Tables 5 to 7, a binder polymer, a photopolymerizable compound, and a photopolymerization initiator containing at least one member selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof, , The resist patterns formed using the photosensitive resin compositions of Examples 1 to 11 containing a nitroxyl compound containing a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure have sensitivity, Resolution, adhesion, and resist hem reduction were all excellent. On the other hand, in Comparative Examples 1 to 7, it was difficult to improve sensitivity, resolution, adhesion, and resist hem reduction.

The photosensitive resin composition of one embodiment of the present disclosure is applied as a material for forming a resist pattern for manufacturing a printed wiring board. In particular, since the photosensitive resin composition has good sensitivity, resolution, adhesion, and resist fade reduction properties, it is used to efficiently manufacture printed wiring boards with high-density wiring such as high-density package substrates and silicon chip rewiring with high precision. It is also suitable for pattern formation.

One… Photosensitive element, 2… Support, 3… Photosensitive resin composition layer, 4... Protective layer, 10… Conductor layer, 15... Insulating layer, 20... Mask, 30… Register pattern, 32… Photosensitive resin composition layer, 40... Conductor pattern, 42… Plating layer.

Claims (9)

(A) Component: binder polymer,
(B) Component: a photopolymerizable compound,
(C) Component: a photopolymerization initiator containing at least one member selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives;
(D) Component: nitroxyl compound,
(E) Component: Contains a phenolic compound,
The component (D) includes a compound having a 2,2,6,6-tetramethylpiperidine-1-oxyl structure,
The component (E) is 2,2-methylene-bis(4-methyl-6-tertiary butylphenol), catechol, picric acid, 4-tertiary-butylcatechol, 2,6-tertiarybutyl-p. - at least one member selected from the group consisting of cresol, and 4,4'-thiobis[ethylene(oxy)(carbonyl)(ethylene)]bis[2,6-bis(1,1-dimethylethyl)phenol] A photosensitive resin composition containing a. In claim 1,
A photosensitive resin composition in which the 2,4,5-triarylimidazole dimer and its derivatives include a compound represented by the following general formula (1).

[In formula (1), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group that may be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5. However, when p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different.] In claim 1 or 2,
A photosensitive resin composition in which the component (A) has a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylic acid. In claim 1 or 2,
(F) Component: The photosensitive resin composition which further contains a sensitizer, and where said (F) component contains a pyrazoline compound. A photosensitive element comprising a support and a photosensitive resin composition layer formed using the photosensitive resin composition according to claim 1 provided on the support. A photosensitive layer forming step of forming a photosensitive resin composition layer on a substrate using the photosensitive resin composition according to claim 1 or the photosensitive element according to claim 5;
An exposure step of irradiating actinic light to at least a portion of the photosensitive resin composition layer and photocuring the region to form a cured product region;
A method of forming a resist pattern having a development step of removing a region of the photosensitive resin composition layer other than the cured product region from the substrate, and forming a resist pattern that is the cured product region on the substrate. In claim 6,
A method of forming a resist pattern, wherein the wavelength of the actinic light is in the range of 340 nm to 430 nm. A method of manufacturing a printed wiring board, comprising the step of etching or plating a substrate on which a resist pattern is formed by the resist pattern formation method according to claim 6. delete

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