JP2010079089A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method capable of obtaining the excellent adhesion of a photosensitive layer to a substrate to be treated, attaining stable sensitivity to improve work efficiency, and forming a pattern with high precision. <P>SOLUTION: In this pattern forming method, a pattern is formed on the surface of a processing object of a substrate to be treated using a pattern forming material including a support and the photosensitive layer stacked on the support. The method includes: a laminate process of vacuum-laminating the pattern forming material on the substrate to be treated with the photosensitive layer facing the surface of the processing object; a separating process of separating the support from the photosensitive layer after the laminate process; and an exposure process of performing the exposure of a desired pattern to the photosensitive layer after the separating process. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pattern forming method, and more particularly to a pattern forming method for efficiently forming a high-definition pattern suitable for a solder resist or the like.

When forming a permanent pattern such as a wiring pattern, a film type pattern forming material in which a photosensitive layer is formed by applying and drying a photosensitive resin composition on a support is used.
As a method for producing the permanent pattern, for example, a laminate is formed by laminating the pattern forming material on a substrate such as a copper clad laminate on which a wiring pattern is formed, and the laminate is formed on the photosensitive layer. After the exposure, the photosensitive layer is developed to form a pattern, and then an etching process or the like is performed to form the permanent pattern.

However, since there are irregularities due to the wiring pattern or the like on the surface of the substrate on which the permanent pattern is formed, bubbles remain between the laminated pattern forming materials, and unbonded portions between the substrate and the pattern forming material Or the embedding property of the pattern forming material in the recesses or gaps deteriorates, and there is a problem that a high-definition permanent pattern cannot be formed.
In addition, due to the presence of an unbonded portion, sufficient adhesion cannot be obtained between the substrate and the pattern forming material, and particularly in the production of a high-definition pattern, the resist formed during development is peeled off. There is. Even when the substrate surface is smooth, the same problem may occur when sufficient adhesion cannot be obtained between the substrate and the pattern forming material.

Therefore, in order to improve the adhesion between the pattern forming material and the substrate, a method of laminating the pattern forming material and the substrate using a vacuum laminator is generally used.
A procedure for forming a pattern on the processing target surface 510A of the printed wiring board 510 as shown in FIG. In FIG. 2A, the printed wiring board 510 includes a substrate 511 and a printed wiring 512 formed on the substrate 511. The printed wiring 512 forms a convex portion on the processing target surface 510A.

First, as shown in FIG. 2B, a pattern forming material 520 provided with a support 521 and a photosensitive layer 522 is printed as a substrate to be processed so that the photosensitive layer 522 is on the processing target surface 510A side. Vacuum lamination is performed on the wiring board 510.
At this time, the oxygen concentration in the photosensitive layer 522 and the vicinity thereof decreases due to evacuation, and the sensitivity of the photosensitive layer 522 is temporarily increased. Become. Therefore, in order to repeatedly and stably form a pattern, after vacuum lamination, the process waits until the sensitivity of the photosensitive layer 522 is stabilized (for example, about 1 hour), and then proceeds to the next step.

In the next step, as shown in FIG. 2C, a desired region of the photosensitive layer 522 is exposed. A cured region 522A is formed in the exposed portion, and the other portion remains as an uncured region 522B. In FIG. 2C, a portion located on the printed wiring 512 is an uncured region 522B.
After that, as shown in FIG. 2D, the support 521 is peeled off and removed. Finally, as shown in FIG. 2E, a desired pattern (cured region 522A) can be formed on the printed wiring board 510 by dissolving and removing the uncured region 522B with a developer.

  However, in such a conventional method, after the vacuum lamination, the photosensitive layer 522 needs to be exposed after waiting until the sensitivity of the photosensitive layer 522 is stabilized. Due to this waiting time (hold time), the tact time becomes longer, and there is a problem that the working efficiency is lowered.

Patent Document 1 proposes a method in which a dry film is bonded to a transparent substrate by a dry film laminating method, a support film is peeled, and then exposed and developed to form a resin layer having a uniform thickness.
Patent Document 2 omits the support film and the protective film, thereby suppressing the generation of laminate voids during the lamination to the substrate and the discharge of dust, and the roll product has the same weight without changing the winding diameter. A support / protection film-less type photosensitive film capable of winding a product has been proposed.
However, the method described in Patent Document 1 and the photosensitive film described in Patent Document 2 are not intended to efficiently form a high-definition pattern using a vacuum laminate. Further, there is no description or suggestion about the problem of the vacuum lamination and the sensitivity stability associated therewith, and the above problem cannot be solved.

  Therefore, a pattern forming method that can form a pattern with high definition and efficiency, has a stable sensitivity, and has high resolution and high adhesion between the substrate to be processed and the photosensitive layer. It is not yet provided, and the current situation is that further improvement and development is desired.

JP 2001-100211 A JP-A-2005-345698

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a pattern forming method capable of obtaining excellent adhesion of a photosensitive layer to a substrate to be processed, having stable sensitivity, excellent work efficiency, and capable of forming a pattern with high definition. To do.

Means for solving the above problems are as follows. That is,
<1> A pattern forming method for forming a pattern on a surface to be processed of a substrate to be processed using a pattern forming material including a support and a photosensitive layer laminated on the support, wherein the photosensitive layer is the processing layer. A laminating step of vacuum laminating the pattern forming material on the substrate to be processed so as to be on the target surface side, a peeling step of peeling the support from the photosensitive layer after the laminating step, And an exposure step of exposing the photosensitive layer to a desired pattern later.
In the pattern forming method according to <1>, the process target surface and the photosensitive layer can be closely adhered to each other by the laminating step. Here, the vacuum lamination increases the sensitivity of the photosensitive layer. However, in the peeling step subsequent to the laminating step, the support is peeled from the photosensitive layer, so that the photosensitive layer is exposed to air and the sensitivity is rapidly increased. Stabilize. Therefore, a state where the surface to be processed and the photosensitive layer are in close contact with each other and the sensitivity of the photosensitive layer is stable is achieved, and the exposure process can be performed at an early stage.
<2> The processing target surface is the pattern forming method according to <1>, wherein the surface is uneven.
<3> The pattern forming method according to <2>, wherein the substrate to be processed is a printed wiring board having printed wiring, and the printed wiring forms unevenness on a surface to be processed.
<4> The exposure amount in the exposure step is 1.1 to 3.0 times the exposure amount in the exposure step when the laminating step, the exposure step, and the peeling step are performed in this order. <1> To <3>.
<5> The laminating step is the pattern forming method according to any one of <1> to <4>, which is performed using a vacuum roll laminator.
<6> The laminating step is the pattern forming method according to any one of <1> to <4>, which is performed using a vacuum press laminator.

<7> The pattern forming method according to any one of <1> to <6>, further including a development step of developing the photosensitive layer after the exposure step.
<8> The pattern forming method according to <7>, further including a permanent pattern forming step of forming a permanent pattern after the developing step.
<9> The pattern forming method according to <8>, wherein after the development, the photosensitive layer is cured.
<10> The pattern forming method according to <9>, wherein the curing process is at least one of an entire surface exposure process and an entire surface heat treatment performed at 120 ° C to 200 ° C.
<11> The pattern forming method according to any one of <8> to <10>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
<12> The pattern forming method according to <8>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.
<13> The pattern forming method according to <12>, wherein the wiring pattern is formed by one of a subtractive method and a semi-additive method.

<14> The pattern forming method according to any one of <1> to <13>, wherein the photosensitive layer includes a polymerizable compound, a binder, and a photopolymerization initiator.
<15> The pattern forming method according to <14>, wherein the photosensitive layer further includes a thermal crosslinking agent.
<16> The above <14> to <15>, wherein the polymerizable compound has at least one selected from a compound containing a propylene oxide group, a compound containing an ethylene oxide group, a compound containing a urethane group, and a compound containing an aryl group. The pattern forming method according to any one of the above.
<17> The pattern forming method according to any one of <14> to <16>, wherein the polymerizable compound includes at least a compound containing a propylene oxide group, a compound containing a urethane group, and a compound containing an aryl group.
<18> The pattern forming method according to any one of <14> to <17>, wherein the polymerizable compound has a bisphenol skeleton.
<19> The pattern forming method according to any one of <14> to <18>, wherein the binder has an acidic group.
<20> The pattern forming method according to any one of <14> to <18>, wherein the binder includes a vinyl copolymer.
<21> The pattern forming method according to any one of <14> to <20>, wherein the binder includes a copolymer of at least one of styrene and a styrene derivative.

<22> The photopolymerization initiator is at least one selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes. The pattern forming method according to any one of <14> to <21>.
<23> The pattern formation method according to <22>, wherein the photopolymerization initiator includes hexaarylbiimidazole.
<24> From <15> above, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 23>.
<25> The pattern forming method according to <24>, wherein the thermal crosslinking agent is an epoxy compound including at least an epoxy group having an alkyl group at the β-position.
<26> The pattern forming method according to any one of <1> to <25>, wherein the photosensitive layer has a thickness of 1 μm to 100 μm.
<27> The photosensitive layer contains 5% by mass to 80% by mass of a binder, 5% by mass to 50% by mass of a polymerizable compound, and 0.1% by mass to 30% by mass of a photopolymerization initiator. The pattern forming method according to any one of <14> to <26>.

<28> The pattern forming method according to any one of <1> to <27>, wherein the support has a long shape.
<29> The pattern forming method according to any one of <1> to <28>, wherein the pattern forming material has a long shape and is wound in a roll shape.
<30> The pattern forming method according to any one of <1> to <29>, wherein a protective film is provided on the photosensitive layer in the pattern forming material.
<31> The above <1> to <30> having a protective film on the photosensitive layer, wherein the protective film contains at least one selected from a polypropylene resin, an ethylene-propylene copolymer resin, and a polyethylene terephthalate resin. The pattern forming method according to any one of the above.

  According to the present invention, the conventional problems can be solved, the object can be achieved, excellent adhesion of the photosensitive layer to the substrate to be processed is obtained, the sensitivity is stable, and the working efficiency is excellent. A pattern forming method capable of forming a pattern with high definition can be provided.

(Pattern formation method)
The pattern forming method of the present invention is a pattern forming method for forming a pattern on a surface to be processed of a substrate to be processed using a pattern forming material including a support and a photosensitive layer laminated on the support, It includes a laminating step, a peeling step, and an exposure step, and further includes other steps that are appropriately selected as necessary.
FIG. 1 shows an outline of the pattern forming method of the present invention.

[Lamination process]
The laminating step is a step of vacuum laminating the pattern forming material on the substrate to be processed such that the photosensitive layer is on the surface to be processed.
There is no restriction | limiting in particular as the method of the said vacuum lamination, Although it can select suitably according to the objective, For example, the method of using a vacuum roll laminator, a vacuum press laminator, etc. is mentioned.
In particular, a method using a vacuum roll laminator is preferable from the viewpoint of tact, and a method using a vacuum press laminator is preferable from the viewpoint of embedding.
There is no restriction | limiting in particular as implementation conditions of the said vacuum lamination, According to the objective, it can select suitably.

  For example, when a pattern is formed on the processing target surface 510A of the printed wiring board 510 as shown in FIG. 1A, in the laminating process, as shown in FIG. 1B, the support 521, the photosensitive layer 522, The pattern forming material 520 having the above is vacuum-laminated on the substrate 510 to be processed so that the photosensitive layer 522 is on the processing target surface 510A side.

[Peeling process]
The peeling step is a step of peeling the support from the photosensitive layer after the laminating step. For example, as shown in FIGS. 1B to 1C, the support 521 is peeled from the photosensitive layer 522.
There is no restriction | limiting in particular as implementation conditions of the said peeling process, According to the objective, it can select suitably.
From the viewpoint of shortening the tact time, the peeling step is preferably performed as soon as possible after the laminating step.

<Substrate to be treated>
The substrate to be treated is not particularly limited and can be appropriately selected from known materials from those having a high surface smoothness to those having an uneven surface. ) And having an uneven surface on the surface to be treated, specifically, known printed wiring boards (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films , Paper, metal plate and the like. The printed wiring board may be a printed wiring board already formed, or may be a printed wiring board forming substrate before the printed wiring is formed.

  Suitable examples of the printed wiring board or the printed wiring board forming substrate include a glass epoxy substrate, an epoxy-impregnated aramid nonwoven fabric, a surface of an insulating layer such as polyimide, and a copper foil layer provided as a plating foil or a sputtered foil. . When the sputter foil is provided, another metal foil (Ni, Cr, etc.) may be provided as a base layer for the purpose of improving the adhesion between the copper foil and the insulating layer.

The surface of the substrate to be treated may be formed with irregularities of about 0.5 to 2 μm by a method such as chemical polishing for the purpose of improving adhesion with the pattern forming material to be laminated.
In the pattern forming method of the present invention, not only the substrate to be processed having high surface smoothness but also the substrate to be processed having an uneven surface can be excellently formed by the vacuum laminating. Embeddability is obtained.

<Pattern forming material>
The pattern forming material is not particularly limited as long as it has at least a photosensitive layer on a support, and can be appropriately selected according to the purpose. The photosensitive layer is preferably formed on a support, and a cushion layer may be provided between the support and the photosensitive layer as long as the effects of the present invention are not impaired. A protective film may be formed on the layer. Furthermore, other layers appropriately selected may be provided.

<< Photosensitive layer >>
The photosensitive layer contains a polymerizable compound, a binder, and a photopolymerization initiator, preferably contains a thermal crosslinking agent, and may contain a sensitizer and other components appropriately selected as necessary.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate are preferable examples, and dipentaerythritol hexa (meth) ) Acrylate is particularly preferred.

  As the polymerizable compound, a monomer or oligomer having at least one of a urethane group and an aryl group may be used. Further, these preferably have two or more polymerizable groups.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.), polymerizable cyclic ether groups (for example, epoxy groups, oxetane groups, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable, for example, paragraph number [0210 of JP-A-2005-258431 ] To [0285].

  As solid content in the said photosensitive layer of the said polymeric compound, 5-50 mass% is preferable, and 10-40 mass% is more preferable. If the solid content is 5% by mass or more, good developability and exposure sensitivity can be obtained, and if it is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

-Binder-
For example, the binder is preferably swellable with respect to an alkaline liquid, and more preferably soluble in an alkaline liquid.
As the binder exhibiting swellability or solubility with respect to the alkaline liquid, for example, those having an acidic group are preferably mentioned.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of adjustment of film properties, and the like. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes (eg styrene, styrene derivatives, etc.), (meth) acrylonitrile, complex substituted with vinyl groups Cyclic groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate ( 2-acryloyl Ciethyl ester), mono (1-methyl-2-acryloyloxyethyl ester) phosphate, vinyl monomers having a functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group), and the like. Among these, the styrenes (styrene and styrene derivatives) are preferable in that a permanent pattern such as a wiring pattern can be formed with high definition and the tent property can be improved.

  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, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

In the Structural Formula (1) ~ (3), R 1 represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ₁ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent an integer of 1 or more.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is 5 mol% or more, the developability to alkaline water is good, and if it is 50 mol% or less, the developer resistance of the cured portion (image portion) is good.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is 2,000 or more, the film has sufficient strength and stable production is possible, and when it is 300,000 or less, the developability is good.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  In addition, as the binder, a resin soluble in an alkaline liquid described in Japanese Patent No. 2873890 can be used.

When the binder is a substance having a glass transition temperature (Tg), the glass transition temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tack and edge of the pattern forming material 80 degreeC or more is preferable, 100 degreeC or more is more preferable, and 120 degreeC or more is especially preferable from the viewpoint of the suppression of a fusion | melting and the at least any one of the peelability improvement of the said support body.
If the said glass transition temperature is 80 degreeC or more, it can prevent that the tack | tuck and edge fusion of the said pattern formation material increase, or the peelability of the said support body deteriorates.

  Examples of the binder further include JP-A Nos. 51-131706, 52-94388, 64-62375, 2-97513, 3-289656, 61-243869. , An epoxy acrylate compound having an acidic group, and a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain, an epoxy acrylate compound and a side chain Examples thereof include a vinyl copolymer having a (meth) acryloyl group and an acid group, and a maleic anhydride copolymer.

  The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained, for example, by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.

  Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; NISSAN CHEMICAL INDUSTRY CO., LTD. "ALALDITE PT810; Ciba Specialty Chemicals" etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, glycidylamine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane), hydantoy Type epoxy resin, cycloaliphatic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals”, etc.), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Co., Ltd., etc.); a polyphenol compound obtained by a condensation reaction of a phenol compound such as phenol, o-cresol, naphthol and an aromatic aldehyde having a phenolic hydroxyl group; D Reaction product with chlorohydrin; Reaction product of polyphenol compound obtained by addition reaction of phenol compound with diolefin compound such as divinylbenzene or dicyclopentadiene and epichlorohydrin; Ring-opening polymerization product of 4-vinylcyclohexene-1-oxide Epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy resin obtained by glycidyl etherification of one kind selected from phenol and cresol and p-hydroxybenzaldehyde condensate; bis (glycidyloxyphenyl) fluore Bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of carboxyl group-containing monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, Acrylic acid dimer; in addition, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride; halogen Examples thereof include reaction products with carboxylic acid compounds, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Furthermore, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1, Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, Maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride , Phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride Dibasic acid anhydrides such as chlorendic anhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride Acids, polybasic acid anhydrides such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid and the like can also be used. These may be used individually by 1 type and may use 2 or more types together.
Each is reacted in order to obtain an epoxy acrylate, and the ratio in which they are reacted is preferably 0.8 to 1.2 equivalents of carboxyl groups of the carboxyl group-containing monomer with respect to 1 equivalent of epoxy groups of the polyfunctional epoxy compound. Is 0.9-1.1 equivalent, 0.1-1.0 equivalent of polybasic acid anhydride, preferably 0.3-1.0 equivalent.

  Also, compounds obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 can be used as the epoxy acrylate of the present invention.

  The molecular weight of the epoxy acrylate compound is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. If the molecular weight is 1,000 or more, the tackiness of the surface of the photosensitive layer becomes strong, and after curing of the photosensitive layer described later, it is possible to prevent the film quality from becoming brittle or the surface hardness from being deteriorated. If it is 100,000 or less, the developability will be good and the synthesis of the resin will be easy.

  An acrylic resin having at least one polymerizable group such as an acidic group or a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as (meth) acrylate group or (meth) acrylamide group, various polymerizations such as carboxylic acid vinyl ester, vinyl ether, allyl ether, etc. Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule and (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate.

  Furthermore, as the binder, a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain can be used. Specifically, for example, (1) a vinyl monomer having an acidic group, (2 ) Obtained by vinyl (co) polymerization of a vinyl monomer having a functional group that can be used for the polymer reaction described later, if necessary, and (3) other copolymerizable vinyl monomer if necessary A polymer is synthesized, and (4) a (meth) acryloyl group and a functional group reactive to at least one of an acidic group in the (co) polymer or a functional group available for polymer reaction It can be obtained by polymer reaction with a compound having

There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has said (1) acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and a monomer having a hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono ( And (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  In the vinyl monomer having a functional group usable for the polymer reaction of (2), the functional group usable for the polymer reaction is a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. Moreover, the carboxyl group and acid anhydride group of the above-mentioned (1) are also mentioned as usable functional groups.

  Examples of the vinyl monomer having a hydroxyl group include compounds represented by the structural formulas (4) to (12).

  Examples of the vinyl monomer having an amino group include vinyl benzylamine and aminoethyl methacrylate.

  Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (1) to (3).

  Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (13).

  However, in said structural formula (13), R represents either H or Me.

Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
Moreover, each said monomer may be used individually by 1 type, and may use 2 or more types together.

  The other copolymerizable monomer used as necessary in (3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters and crotonic acid. Esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2 -Methylpropanesulfonic acid, Vinyl monomers having mono (2-acryloyloxyethyl ester) acid, mono (1-methyl-2-acryloyloxyethyl ester) phosphate, and functional groups (for example, urethane group, urea group, sulfonamide group, imide group) Etc.

  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, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene Glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dis Clopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, And tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include the styrene, the styrene derivatives (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, Bromostyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like).

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing a vinyl monomer having a urethane group or a urea group as the functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, a monomer having an isocyanate group, and a hydroxyl group An addition reaction with a compound containing 1 or a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate. .

Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (1) to (3), as in the above-described (2).
Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.
Examples of the monomer having a hydroxyl group include compounds represented by the structural formulas (4) to (12) in the same manner as shown in (2) above.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
By vinyl (co) polymerizing these, (co) polymers containing acid groups, acid anhydride groups and, if necessary, hydroxyl groups, amino groups, isocyanate groups, epoxy groups, acid halide groups, active halide groups, etc. can get. The vinyl (co) polymer can be prepared by copolymerizing corresponding monomers according to a conventional method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.
With respect to the (co) polymer thus obtained, as the above (4), an acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It is obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) acryloyl group.

As the compound having a (meth) acryloyl group and a functional group reactive to at least one of the acidic group in the (co) polymer of the above (4) or a functional group available for polymer reaction The compounds shown in (2) above can be used.
Examples of combinations of functional groups in performing these polymer reactions include, for example, a combination of a copolymer having an acidic group (such as a carboxyl group) and a vinyl monomer having an epoxy group, and a copolymer having an amino group and an epoxy group. A combination of vinyl monomers having an amino group, a combination of a copolymer having an amino group and a vinyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a vinyl monomer having an isocyanate group, a copolymer having a hydroxyl group and an acid halide group A combination of vinyl monomers having an amino group, a combination of a copolymer having an amino group and a vinyl monomer having an active halide group, a combination of a copolymer having an acid anhydride group and a vinyl monomer having a hydroxyl group, a copolymer having an isocyanate group Combination of coalesce and vinyl monomer having amino group, isocyanate group Combinations of vinyl monomer having a copolymer and a hydroxyl group of the combination of the vinyl monomer having a copolymer and an amino group having an active halide groups, and the like. Two or more of these combinations may be used in combination.

Examples of commercially available binders include “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, and “CYCLOMER M”. -200; Daicel Chemical Industries, Ltd. "," Lipoxy SPC-1X, Lipoxy SPC-2X, Lipoxy SPC-3X; Showa High Polymer Co., Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Polyimide precursors described in Japanese Patent Laid-Open No. 11-282155, and the like can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is preferably 3,000 to 500,000, 5,000-100,000 are more preferable. If the molecular weight is 3,000 or more, the tackiness of the surface of the photosensitive layer becomes strong, and after curing of the photosensitive layer described later, the film quality becomes brittle, or the surface hardness can be prevented from being deteriorated, If it is 500,000 or less, the developability will be good.

As the binder, a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer can also be used. The copolymer is a maleamic acid-based copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A not having the maleic acid half amide structure, represented by the following structural formula (14). It is preferably a coalescence.
The unit A may be one type or two or more types. For example, assuming that the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

In the Structural Formula (14), R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (14), as R ¹ , for example, (—COOR ¹⁰ ), (—CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (—OCOR ¹³ ), (—OR ¹⁴ ), substituents such as (—COR ¹⁵ ). Here, said R < ¹⁰ > -R < ¹⁵ > represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10 to} R ¹⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ¹ include benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl; n-propyloxycarbonyl, n- Examples include butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

Examples of R ² include an alkyl group, an aryl group, and an aralkyl group that may have a substituent. These may have a cyclic structure or a branched structure. Specific examples of R ² include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, α-methylbenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4- Chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) ethyl, -Fluoro-α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, ethyl, propyl I-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl , 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine and the like.

  The binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the vinyl monomer. ) Is preferably a copolymer obtained by reacting a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature of less than 80 ° C. A copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. Moreover, in the copolymer which consists of this (a) component and this (c) component, although lamination property can be ensured, it may become difficult to ensure the said surface hardness.

-(B) Aromatic vinyl monomer-
The aromatic vinyl monomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the surface hardness of the photosensitive layer formed using the pattern forming material of the present invention can be increased. In this respect, a compound having a glass transition temperature (Tg) of the homopolymer of 80 ° C. or higher is preferable, and a compound of 100 ° C. or higher is more preferable.
Specific examples of the aromatic vinyl monomer include styrene (homopolymer Tg = 100 ° C.), α-methylstyrene (homopolymer Tg = 168 ° C.), 2-methylstyrene (homopolymer Tg = 136 ° C.). ), 3-methylstyrene (homopolymer Tg = 97 ° C.), 4-methylstyrene (homopolymer Tg = 93 ° C.), 2,4-dimethylstyrene (homopolymer Tg = 112 ° C.) Preferably mentioned. These may be used individually by 1 type and may use 2 or more types together.

-(C) Vinyl monomer--
The vinyl monomer needs to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C., preferably 40 ° C. or less, and more preferably 0 ° C. or less.
Examples of the vinyl monomer include n-propyl acrylate (homopolymer Tg = −37 ° C.), n-butyl acrylate (homopolymer Tg = −54 ° C.), pentyl acrylate, or hexyl acrylate (homopolymer acrylate). Tg = −57 ° C.), n-butyl methacrylate (Tg of homopolymer = −24 ° C.), n-hexyl methacrylate (Tg of homopolymer = −5 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.

-Primary amine compound-
Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chloro Benzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- ( 3-Chlorophenyl) ethyla Min, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, propylamine, 1 -Propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, anisi Gin, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3- Examples thereof include propoxypropylamine and 3-isopropoxypropylamine. Among these, benzylamine and phenethylamine are particularly preferable.
The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

  The reaction amount of the primary amine compound needs to be 0.1 to 1.2 equivalents relative to the anhydride group, and preferably 0.1 to 1.0 equivalents. When the reaction amount is 1.2 equivalents or less, it is possible to prevent the solubility from being significantly deteriorated when at least one primary amine compound is reacted.

  The content of the (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, particularly preferably 20 to 40 mol%. If the content is 15 mol% or more, alkali developability can be imparted, and if it is 50 mol% or less, good alkali resistance can be obtained, and the synthesis of the copolymer is facilitated. A permanent pattern can be formed. In this case, the content of the vinyl monomer in which the glass transition temperature (Tg) of the (b) aromatic vinyl monomer and (c) homopolymer is less than 80 ° C. 20-60 mol% and 15-40 mol% are preferable. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), a compound obtained by reacting an anhydride group of the maleic anhydride copolymer with a primary amine compound, or a binder such as a polyimide precursor, 3,000 to 500,000 are preferable, and 5,000 to 100,000 are more preferable. If the molecular weight is 3,000 or more, the tackiness of the surface of the photosensitive layer becomes strong, and it is possible to prevent the film quality from becoming brittle or the surface hardness from being deteriorated after curing of the photosensitive layer described later. If it is below, developability will become favorable.

  As solid content in the said photosensitive layer of the said binder, 5-80 mass% is preferable, and 10-70 mass% is more preferable. When the solid content is 5% by mass or more, the film strength of the photosensitive layer and the tackiness of the surface of the photosensitive layer are good, and when it is 50% by mass or less, the exposure sensitivity is good.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is visible from the ultraviolet region. It is preferable to have photosensitivity to the light of the photocatalyst, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and initiates cationic polymerization depending on the type of monomer. Initiator may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, and the like. Examples thereof include oxides, thio compounds, ketone compounds, aromatic onium salts, and metallocenes.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2, 6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1, 3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) Examples include -4,6-bis (tribromomethyl) -s-triazine.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4 Oxadiazole and the like).

  Examples of the phosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, and the like. Is mentioned.

Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (3-methoxyphenyl) ) Biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4-methoxyphenyl) -4 , 4 ', 5,5'-tetraphenylbi Dazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-trifluoromethylphenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, compounds described in WO00 / 52529, and the like.
The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

  Examples of the oxime derivative include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

Examples of the organic peroxide include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone.
Examples of the thio compound include 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-benzoylmethylene-3-methylnaphthothiazoline, and the like.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bis (dicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Benzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-dimethyl Amino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1 -Methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, Jill dimethyl ketal), and the like.

Examples of the aromatic onium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, tetraphenylphosphonium-hexafluorophosphate, and the like.
Examples of the metallocenes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-), and the like.

  Further, as photopolymerization initiators other than the above, N-phenylglycine and other polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethyl ketone, etc.), amines (for example, 4-dimethylamino) Ethyl benzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-phthalimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4 -Dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-di- Tilaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N- Methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), JP-A-53-133428, JP-B-57-1819, Examples thereof include compounds described in JP-A-57-6096 and US Pat. No. 3,615,455.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
As a particularly preferable example of the photopolymerization initiator, a combination of the phosphine oxides, the halogenated hydrocarbon compound having the triazine skeleton, and an amine compound, which can be applied to laser light having a wavelength of 405 nm in the later-described exposure. Composite photoinitiators, hexaarylbiimidazole compounds, hexaarylbiimidazole compounds and hetero-fused compounds, or metallocenes.
Furthermore, a chain transfer agent (for example, a mercapto compound, more specifically 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, etc.) may be used in combination with these initiators.

  As content in the said photosensitive layer of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

-Thermal crosslinking agent-
When the pattern forming material is used for a solder resist or the like, a thermal crosslinking agent may be included in the photosensitive layer. The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the pattern forming material, developability, etc. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy compound having at least two oxirane rings in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resins, novolac type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenols A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, odor Phenol novolac type epoxy resin), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.” HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin A reaction product of 4-vinylcyclohexene-1-oxide obtained by epoxidation with peracetic acid or the like, an epoxy resin having a linear phosphorus-containing structure, an epoxy resin having a cyclic phosphorus-containing structure, α-methylstilbene Type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP- 5 0S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane rings in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is a β-alkyl-substituted glycidyl group in all the epoxy groups in the total amount of the epoxy compound contained in the photosensitive layer. Is preferably 70% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the pattern forming material and the ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol F Bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate and the like, and C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formalde De polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; dihydroxynaphthalene Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ethers of binaphthol, di-β-alkyl glycidyl ethers of binaphthol; poly- of phenol-formaldehyde polycondensates β-alkyl glycidyl ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate Bisphenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether; phenol compound-divinylbenzene polyaddition product poly-β-alkyl glycidyl ether; The
Among these, a bisphenol compound represented by the following structural formula (i), a β-alkyl glycidyl ether derived from a polymer obtained from this and epichlorohydrin, and the following structural formula (ii) Poly-β-alkyl glycidyl ethers of phenol compound-formaldehyde polycondensates are preferred.

However, in said structural formula (i), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
In the Structural Formula (ii), R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R "represents any one of hydrogen atom, and CH _3, n is 0 Represents an integer of ~ 20.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds with hydroxyl group resins such as silsesquioxane, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

Moreover, in order to accelerate the thermosetting of the epoxy resin compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole and 2-ethylimidazole 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Imidazole derivatives Bicyclic amidine compounds and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2- Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid addition S-triazine derivatives such as products can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
The solid content in the photosensitive layer of the epoxy resin, the oxetane compound, and a compound capable of accelerating thermal curing of these with a carboxylic acid is usually 0.01 to 15% by mass.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; the bifunctional isocyanate and trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as sulphonate and derivatives thereof; and the like.

Furthermore, for the purpose of improving the storage stability of the pattern forming material of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols such as isopropanol and tertiary butanol; lactams such as ε-caprolactam; phenol, cresol, p-tertiary butylphenol, p-secondary butylphenol, p-secondary amylphenol, and p-octylphenol. Phenols such as p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; active methylene compounds such as dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime and cyclohexanone oxime And the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  As content in the said photosensitive layer of the said thermal crosslinking agent, 1-50 mass% is preferable, and 3-30 mass% is more preferable. When the solid content is 1% by mass or more, the film strength of the cured film is improved, and when the solid content is 50% by mass or less, it is possible to prevent a decrease in developability and a decrease in exposure sensitivity.

-Other ingredients-
Examples of the other components include sensitizers, thermal polymerization inhibitors, surfactants, plasticizers, color formers, colorants, and the like, and adhesion promoters and other auxiliaries for the surface of the substrate to be treated. (For example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) May be. Further, by appropriately containing these components, properties such as stability, photographic properties, film physical properties and the like of the target pattern forming material can be adjusted.
Among these, in the case of exposing and developing the photosensitive layer, from the viewpoint of improving the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development, for example, It is particularly preferable to use a sensitizer together.

--- Sensitizer--
There is no restriction | limiting in particular as said sensitizer, According to the said light irradiation means (For example, visible light, an ultraviolet light, visible light laser etc.), it can select suitably. When the light irradiation means is combined with a laser of 380 to 420 nm, a sensitizer having a maximum absorption wavelength of 380 to 450 nm is preferable.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
There is no restriction | limiting in particular as said sensitizer, It can select suitably from well-known sensitizers, For example, a hetero condensed ring type compound is preferable. The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound, a quinoline compound, and an acridine compound.
Specific examples of the hetero-fused ketone compound include acridone compounds such as, for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylami Coumarin, 3- (4-Diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazole-2- Ircoumarin, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363208 And coumarins such as coumarin compounds described in JP 2002-363209 A, and the like.
Specific examples of the quinoline compound include quinoline, 9-hydroxy-1,2-dihydroquinolin-2-one, 9-ethoxy-1,2-dihydroquinolin-2-one, and 9-dibutylamino- 1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-mercaptoquinoline, quinoline-2-carboxylic acid, and the like.
Specific examples of the acridine compound include 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, acridine orange, chloroflavin, and acriflavine. Among these hetero condensed ring compounds, those containing a nitrogen element in the ring are more preferable. Preferred examples of the compound containing a nitrogen element in the ring include the acridine compound, a coumarin compound substituted with an amino group, and an acridone compound. Among these, the acridone, coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferable, and among these, the acridone is particularly preferable.
Also known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squalium (for example, squalium), and the like.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

As content of the said sensitizer, 0.01-4 mass% is preferable with respect to all the components of a photosensitive layer, 0.02-2 mass% is more preferable, 0.05-1 mass% is especially preferable.
If the said content is 0.01 mass% or more, a sensitivity will become favorable, and if it is 4 mass% or less, the shape of a pattern will become favorable.

--- Thermal polymerization inhibitor ---
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and 0.01 to 1% by mass with respect to the polymerizable compound of the photosensitive layer. % Is particularly preferred.
When the content is 0.001% by mass or more, stability during storage is good, and when the content is 5% by mass or less, sensitivity to active energy rays is good.

--Plasticizer--
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, amides such as Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

--Coloring agent--
The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have an oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane but can be oxidized to a coloring compound; Leucoin digoid pigment; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (for example, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediaminetriphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4- Chlorophenyl) ethane); halogenated alcohol compounds (eg, 2,2,2-trichloroethanol, Bromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol, etc .; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (for example, 2-bromoethyl methyl ether, 2-bromoethyl ethyl) Ether, di (2-bromoethyl) ether, 1,2 Halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β) Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); a compound having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-ni B phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive layer. . Moreover, as content of the said halogen compound, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive layer, and 0.005-1 mass% is more preferable.

--Colorant--
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, known pigments or dyes such as red, green, blue, yellow, purple, magenta, cyan, and black may be used. Specifically, Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146) ), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (C.I. Pigment black 1) and carbon black.

  The colorant further includes C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 83, C.I. I. Pigment violet 23, and those described in JP-A-2002-162752 (0138) to (0141). There is no restriction | limiting in particular as an average particle diameter of the said coloring agent, Although it can select suitably according to the objective, For example, 5 micrometers or less are preferable and 1 micrometer or less is more preferable.

--- Dye--
In the photosensitive layer, a dye can be used for the purpose of coloring the photosensitive resin composition for pattern forming material for improving the handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuchsin, oil blue # 603 (Orien Chemical Co., Ltd.), Rhodamine B, Rhodamine 6G, etc. Victoria Pure Blue BOH can be cited, among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid. Anion) and the like.

  As content of the said dye, 0.001-10 mass% is preferable with respect to all the components of the said photosensitive layer, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable.

-Adhesion promoter-
In order to improve the adhesion between the layers or the adhesion between the pattern forming material and the substrate to be processed, a known so-called adhesion promoter can be used for each layer.

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  As content of the said adhesion promoter, 0.001-20 mass% is preferable with respect to all the components of the said photosensitive layer, 0.01-10 mass% is more preferable, 0.1-5 mass% is especially preferable. preferable.

  The photosensitive layer is, for example, J.I. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

--Surfactant--
In order to improve the surface unevenness generated when the pattern forming material of the present invention is produced, a known surfactant can be added.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As content of the said surfactant, 0.001-10 mass% is preferable with respect to all the components of a photosensitive layer.
If the content is 0.001% by mass or more, the effect of improving the surface condition is obtained.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

<< Support >>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of the length of 10-20,000 m is mentioned.

<< Protective film >>
The pattern forming material may form a protective film on the photosensitive layer.
The material contained in the protective film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polypropylene resin, polyethylene resin, ethylene-propylene copolymer resin, polyethylene terephthalate resin, and the support. And the like to be used. These may be used alone or in combination of two or more. The protective film may be a laminated film formed by laminating two or more layers. As the laminated film, for example, a laminated film in which a polypropylene resin film and an ethylene-propylene copolymer resin film are laminated is suitable. It is mentioned in.

  Examples of commercially available protective films include Oji Paper Co., Ltd., Alphan E-501, MA-410, E-200; Teijin Limited, PS series (PS-25, etc.); GF-1, GF-3, GF-8, etc. are mentioned. Moreover, it is also possible to manufacture the said protective film by carrying out the sandblast process of the commercially available film.

  There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable.

The protective film may be surface-treated to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.
When the protective film is used, for example, the adhesive force A of the layer adjacent to the photosensitive layer and the photosensitive layer and other than the protective film and the adhesive force B of the photosensitive layer and the protective film are the adhesive force A>. The relationship of the adhesive force B is preferable.

  Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
If the static friction coefficient is 0.3 or more, it is possible to prevent winding deviation from occurring when the roll is formed due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll. It is.

<< Other layers >>
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, layers, such as a cushion layer, a barrier layer, a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer, are mentioned. . The pattern forming material may have one kind of these layers or two or more kinds. Moreover, you may have two or more layers of the same kind.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer (henceforth a thermoplastic resin layer), It can select suitably according to the objective, Swelling thru | or soluble with respect to an alkaline liquid may be sufficient, and it is insoluble. There may be.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or less, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less as issued on the 25th), those soluble in an alkaline solution are mentioned. In addition, even in an organic polymer material having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer material are added to the organic polymer material so that the substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  In addition, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. With such an interlayer adhesive strength, only the support is peeled off from the laminate, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. be able to. Alternatively, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the laminate, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate Examples thereof include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in the alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is an essential copolymer component of ethylene.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate A copolymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesive strength of the pattern forming material is not particularly limited and can be appropriately selected depending on the purpose. For example, the interlayer adhesive strength of each layer Among them, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. By setting such an interlayer adhesive strength, the support and the cushion layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer can be peeled from the laminate, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

There is no restriction | limiting in particular as an ethylene copolymerization ratio in the copolymer which uses the said ethylene as an essential copolymerization component, According to the objective, it can select suitably, For example, 60-90 mass% is preferable, and 60-80 % By mass is more preferable, and 65 to 80% by mass is particularly preferable.
When the copolymerization ratio of ethylene is 60% by mass or more, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes high, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. If it is 90% by mass or less, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, and the cushion layer and the photosensitive layer are very easily peeled, It is possible to prevent the production of the pattern forming material including the cushion layer from becoming difficult.

There is no restriction | limiting in particular in the thickness of the said cushion layer, According to the objective, it can select suitably, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
If the thickness is 5 μm or more, unevenness on the surface of the substrate to be processed and unevenness followability to bubbles and the like can be improved, and a high-definition permanent pattern can be formed. Can be prevented from increasing.

  It is preferable that the pattern forming material is wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular as length of the said elongate pattern formation material, For example, it can select suitably from the range of 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. The roll-shaped pattern forming material may be slit into a sheet shape. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. Things are preferable.

<< Pattern Forming Material Manufacturing Method >>
The pattern forming material can be manufactured, for example, as follows.
First, the material contained in the photosensitive layer is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution.

  There is no restriction | limiting in particular as said photosensitive resin composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol etc. Alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and other ketones; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy Esters such as propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene, etc. Halogenated hydrocarbons; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive resin composition solution is applied onto the support and dried to form a photosensitive layer, whereby a pattern forming material can be produced.

The method for applying the photosensitive resin composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

[Exposure process]
The exposure step is a step of exposing a desired pattern to the photosensitive layer after the peeling step. For example, as shown in FIG. 1D, a desired region of the photosensitive layer 522 is exposed. A cured region 522A is formed in the exposed portion, and the other portion remains as an uncured region 522B. In FIG. 1D, a portion located on the printed wiring 512 is an uncured region 522B.
From the viewpoint of shortening the tact time, the exposure step is preferably performed as soon as possible after the stripping step.
There is no restriction | limiting in particular as an exposure method, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. It is preferable to use.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation means for irradiating light, and the light irradiation means for irradiating based on the pattern information to be formed. Examples thereof include light modulation means for modulating light.

The exposure amount in the exposure step is 1.1 with respect to the exposure amount in the exposure step when the laminating step, the exposure step, and the peeling step are performed in this order (that is, the exposure amount in the conventional pattern forming method). It is preferably not less than twice and not more than 3.0 times, more preferably not less than 1.5 times and not more than 2.5 times, and particularly preferably not less than 1.8 times and not more than 2.2 times.
In the pattern formation method of this invention, the said peeling process is implemented before the said exposure process, and the said photosensitive layer is exposed to air. As a result, the sensitivity of the photosensitive layer is rapidly stabilized, but on the other hand, the sensitivity is also lowered. In order to cope with this decrease in sensitivity, it is necessary to increase the amount of exposure in the exposure step as compared with the conventional case.
If the exposure amount in the exposure step is 1.1 times or more of the conventional exposure amount, sufficient curing can be obtained, and if high-definition development is possible and the exposure amount is 3.0 times or less, the pattern is destroyed by overexposure. Can be prevented.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, a hardening process process, etc. are mentioned.

<Development process>
The development step is a step of forming a pattern by exposing the photosensitive layer in the pattern forming material by the exposure step, curing the exposed region of the photosensitive layer, and then developing to remove an uncured region. is there. For example, as shown in FIG. 1E, a desired pattern (cured region 522A) can be formed on the printed wiring board 510 by removing the uncured region 522B by swelling and peeling with a developer.

  There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

<Curing process>
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, According to the objective, it can select suitably, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the photosensitive laminate on which the pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, According to the objective, it can select suitably, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the photosensitive laminate on which the pattern is formed after the developing step. The whole surface heating increases the film strength of the surface of the pattern.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. If the heating temperature is 120 ° C. or higher, the film strength can be improved by heat treatment. If the heating temperature is 250 ° C. or lower, the film quality is prevented from becoming weak and brittle due to decomposition of the resin in the photosensitive composition. it can.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate to be processed is a printed wiring board such as a multilayer wiring board, the pattern of the present invention can be formed on the printed wiring board, and soldering can be performed as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist. When the pattern formed by the pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, and in particular, in the case of the interlayer insulating film, For example, it is useful for high-density mounting of semiconductors and components on multilayer wiring boards and build-up wiring boards.

The pattern forming method of the present invention can also be used for forming a wiring pattern. In this case, examples of the other processes include an etching process and a plating process.
For example, when a printed wiring board is manufactured, when the manufacturing is performed by a subtractive method, an etching process is performed after the developing process, and when performed by a semi-additive method, a plating process and an etching process are performed after the developing process. Is done.

<Etching process>
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
By removing the pattern after performing the etching process in the etching step, a permanent pattern can be formed on the surface of the substrate to be processed.
There is no restriction | limiting in particular as said permanent pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.

<Plating process>
The plating step can be performed by a method appropriately selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow 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.
A permanent pattern can be formed on the surface of the substrate to be processed by removing the pattern after plating by the plating step and further removing unnecessary portions by etching or the like as necessary.

[Method of manufacturing printed wiring board]
The pattern forming method of the present invention can also be suitably used for manufacturing a printed wiring board. Hereinafter, an example of the manufacturing method of the printed wiring board using the pattern formation method of this invention is demonstrated.

(1) Laminating process First, a printed wiring board forming substrate having a through hole and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper-clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer A substrate (laminated substrate) on which is formed can be used.
Next, when the protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. The forming material is vacuum laminated on the printed wiring board forming substrate.

(2) Peeling Step After the laminating step, the support of the pattern forming material is peeled from the photosensitive layer.
(3) Exposure Step Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate (from the pattern forming material surface).

(4) Development process The uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with a suitable developer, and the pattern of the cured layer in the wiring pattern formation region and the cured layer in the tent formation region And a metal layer is exposed on the surface of the printed wiring board forming substrate.
Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

(5) Wiring part forming step Thereafter, using the formed pattern, a method of peeling the cured photosensitive layer after etching the printed wiring board forming substrate (for example, a subtractive method) or a plating process Then, the cured photosensitive layer is peeled off, and an unnecessary copper foil layer may be processed by a method of etching (for example, a semi-additive method).
Among these, in order to form a printed wiring board with industrially advantageous tenting, the subtractive method is preferable, but in order to form a pattern with higher resolution (small line / space), A semi-additive process is preferred.

  There is no restriction | limiting in particular as etching liquid which performs the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, chloride, A ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like can be given. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.

In order to peel the cured photosensitive layer, it is treated with a strong alkaline aqueous solution or the like, and removed as a peeled piece from the printed wiring board.
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

The printed wiring board may be a multilayer printed wiring board.
The pattern forming material may be used not only for the above etching process but also for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow 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.

  The pattern forming method of the present invention is suitably used as a pattern forming method capable of obtaining excellent adhesion of a photosensitive layer to a substrate to be processed, having a stable sensitivity and excellent work efficiency, and capable of forming a pattern with high definition. be able to.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
<Manufacture of pattern forming material>
A photosensitive resin composition solution having the following composition is applied on a 16 μm-thick polyethylene terephthalate film (Toray Co., Ltd., 16QS52) as the support and dried to form a photosensitive layer having a thickness of 30 μm on the support. Then, the pattern forming material was manufactured.

[Composition of photosensitive resin composition solution]
-Phenothiazine 0.0049 parts by mass-Methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio):
29/19/52, mass average molecular weight: 60,000, acid value 189)
11.8 parts by mass-5.6 parts by mass of a polymerizable monomer represented by the following structural formula (15)-1 / of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate
2 molar ratio adduct 5.0 parts by mass. 0.56 parts by weight of dodecapropylene glycol diacrylate. 2,2-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 1.7 Parts by mass, 10-butyl-2-chloroacridone 0.09 parts by mass, malachite green oxalate 0.016 parts by mass, leuco crystal violet 0.1 parts by mass, methyl ethyl ketone 40 parts by mass, 1-methoxy-2-propanol 20 parts by mass / Fluorine-based surfactant (Dainippon Ink, F780F)
0.021 part by mass The phenothiazine is the polymerization inhibitor and is a compound having an aromatic ring, a heterocyclic ring, and an imino group in the molecule.

  However, in Structural Formula (15), m + n represents 10.

  A 12 μm-thick polypropylene film (manufactured by Oji Paper Co., Ltd., Alphan-501) was laminated as the protective film on the photosensitive layer of the pattern forming material.

<Lamination process>
A vacuum laminator (manufactured by Meiki Seisakusho, MVLP500) is used with a glass substrate or silicon wafer as the substrate to be processed, and the photosensitive layer of the pattern forming material is in contact with the glass substrate or silicon wafer, while removing the protective film on the pattern forming material. ) To prepare a laminate in which the glass substrate or silicon wafer, the photosensitive layer, and the support were laminated in this order. The pressure bonding conditions were a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.4 MPa, and a vacuum pressing time of 35 seconds (vacuum arrival time of 15 seconds, vacuum pressing time of 20 seconds, no flat pressing).

<Peeling process>
After the laminating step, the mixture was allowed to stand at room temperature for 1 minute, and then the polyethylene terephthalate film (support) was peeled off from the laminate.

<Exposure process>
The photosensitive layer was exposed using a pattern forming apparatus.
The exposure intensity is 30 mJ (exposure time 30 seconds). This is 1.0 times the exposure amount in the exposure process when the lamination process, the exposure process, and the peeling process are performed in this order.

<< Pattern Forming Apparatus >>
An exposure apparatus (model number: INPREX, manufactured by FUJIFILM Corporation) provided with a light irradiation means, a light modulation means, and a microlens array was used as a pattern forming apparatus.
Here, the light modulation means has a plurality of picture element portions for modulating and emitting the light received from the light irradiation means. A plurality of microlenses are arranged in the microlens array, and each microlens has an aspherical surface (toric surface) that can correct aberration of light emitted from the pixel portion.
Specifically, the light irradiation means is a combined laser light source, and the light modulation means is a DMD (digital micromirror device). The DMD includes a microlens array in which microlenses 474 whose one surface is a toric surface are arranged in an array.

<Development process>
Using a 1% Na ₂ CO ₃ aqueous solution at 30 ° C., development was performed in a shower system (0.15 MPa) for a period of 30 to 60 seconds. Then, it was washed with industrial water (no temperature control around 25 ° C.) for 60 seconds to 120 seconds.

<Evaluation>
The produced pattern was evaluated as follows.

<< Evaluation of sensitivity stability >>
By the above-described manufacturing method and the conventional manufacturing method in which the laminating step, the exposure step, and the peeling step are performed in this order, the time from the execution of the laminating step to the execution of the exposure step is varied as follows, and L / S = A 50/50 μm pattern was prepared and the line width was evaluated.

<< Line Tact >>
The time from the start of the lamination process to the end of the exposure process was measured and used as a line tact.

<< Sensitivity of photosensitive layer >>
After the development process, the following three levels were evaluated based on the number of steps.
ΔOD = 0.05 ○: Clear 22 to 23 steps Δ: Clear 24 to 25 steps ×: Clear 26 steps or more

<< embeddability >>
The adhesion to the substrate was visually observed and evaluated according to the following criteria.
○: There are no bubbles and no wrinkles, and they are in good contact.
Δ: There are no wrinkles, but bubbles are mixed.
× ・ ・ ・ There are wrinkles and air bubbles are mixed.
In Examples and Comparative Examples described later using a copper-clad laminate as a base material, the embedded state of the photosensitive layer between L / S / L = 500/100/500 μm wiring patterns was visually observed, and Evaluation was made according to the criteria.
○: There are no bubbles or wrinkles, and it is well embedded.
Δ: There are no wrinkles, but bubbles are mixed.
× ・ ・ ・ There are wrinkles and air bubbles are mixed.

<< Pattern resolution >>
The pattern line width of L / S = 50/50 μm was measured (observed) and evaluated in the following three stages.
○: 50 μm or more and less than 54 μm Δ: 54 μm or more and less than 56 μm ×: 56 μm or more

<< Pattern adhesion >>
L: S = 1: 5 patterns (L = 10 to 100 μm in increments of 10 μm) were measured (observed) and evaluated in the following three stages.
○: L = ˜less than 35 μm Δ: L = 35 μm or more and less than 45 μm ×: L = 45 μm or more

(Example 2)
In Example 1, a pattern was formed and evaluated in the same manner as in Example 1 except that the exposure intensity in the exposure step was changed and the exposure amount was changed from 1.0 times to 3.1 times.

(Example 3)
In Example 1, a pattern was formed and evaluated in the same manner as in Example 1 except that the exposure intensity in the exposure process was changed and the exposure amount was changed from 1.0 to 1.1.

Example 4
In Example 1, a pattern was formed and evaluated in the same manner as in Example 1 except that the exposure intensity in the exposure process was changed and the exposure amount was changed from 1.0 times to 2.0 times.

(Example 5)
In Example 1, a pattern was formed and evaluated in the same manner as in Example 1 except that the exposure intensity in the exposure step was changed and the exposure amount was changed from 1.0 times to 3.0 times.

(Example 6)
In Example 1, a pattern was formed and evaluated in the same manner as in Example 1 except that the substrate to be treated was replaced with the following copper-clad laminate.
<Preparation of copper-clad laminate>
Laminated DFR film on polished, washed and dried copper plate, exposed and developed to form L / S / L = 500/100/500 μm pattern, then etched copper plate and peeled cured film As a result, a copper clad laminate having no wiring pattern 501a on the surface (no through-hole, copper thickness 30 μm) was formed. The formation height of the wiring pattern 501a is 30 μm.

(Example 7)
In Example 6, a pattern was formed and evaluated in the same manner as in Example 6 except that the exposure amount in the exposure step was changed from 1.0 times to 2.0 times.

(Example 8)
In Example 6, a pattern was formed and evaluated in the same manner as in Example 6 except that the laminating step was performed using a vacuum roll laminator.

(Comparative Example 1)
In Example 6, a pattern was formed in the same manner as in Example 6 except that the laminating step, the exposing step, and the peeling step were performed in this order.
In addition, when the exposure process was performed 1 minute after the lamination process, the sensitivity of the photosensitive layer was not stable, and the line width of L / S = 50/50 was 62 μm. Then, the exposure process was carried out. As a result, the tact time was 61 minutes 20 seconds.

(Comparative Example 2)
In Example 6, a pattern was formed and evaluated in the same manner as in Example 6 except that the laminating step was performed with a non-vacuum press laminator under the conditions of 70 ° C., pressing pressure of 0.4 MPa, and press for 20 seconds.

(Comparative Example 3)
In Example 6, a pattern was formed and evaluated in the same manner as in Example 6 except that the laminating step was performed using a roll laminator that was not vacuum.
The results of evaluation in each of the above-described examples and comparative examples are shown in Table 2 below.
Table 3 below shows the time required for the laminating process using various laminators.

From Table 2, in Examples 1 to 8 using the pattern forming method of the present invention, the surface to be processed and the photosensitive layer are in close contact with each other, and the state in which the sensitivity of the photosensitive layer is stabilized at an early stage is achieved. It can be seen that it can be shortened.
On the other hand, in Comparative Example 1 using the conventional method of performing the peeling process after the exposure process, it takes a long time to stabilize the sensitivity of the photosensitive layer, and the tact time is extremely long. Recognize.
Moreover, it turns out that sufficient embedding is not obtained in Comparative Examples 2 and 3 using a laminator which is not vacuum.

From the comparison of Examples 1 to 5, it can be seen that good pattern resolution and pattern adhesion can be obtained when the exposure dose is in the range of 1.1 to 3.0 times.
Further, from Examples 6 and 7, it can be seen that according to the pattern forming method of the present invention, good embedding property can be obtained even if the substrate has irregularities such as a wiring pattern.
In Example 8, the execution time of the lamination process by the vacuum press laminator is 50 seconds, whereas the execution time of the lamination process by the vacuum roll laminator is 20 seconds. Therefore, the tact time is reduced by 30 seconds compared to Example 6. did.

  The pattern forming method of the present invention is suitably used as a pattern forming method capable of obtaining excellent adhesion of the photosensitive layer to the substrate to be processed, having stable sensitivity, excellent work efficiency, and capable of forming a pattern with high definition. be able to.

FIG. 1 is a diagram showing an outline of the pattern forming method of the present invention. FIG. 2 is a diagram showing an outline of a conventional pattern forming method.

Explanation of symbols

510 Printed wiring board (substrate to be processed)
510A Surface to be treated 511 Substrate 512 Printed wiring 520 Pattern forming material 521 Support 522 Photosensitive layer 522A Cured region 522B Uncured region

Claims (10)

A pattern forming method for forming a pattern on a surface to be processed of a substrate to be processed using a pattern forming material including a support and a photosensitive layer laminated on the support,
A laminating step of vacuum laminating the pattern forming material on the substrate to be processed so that the photosensitive layer is on the surface to be processed;
A peeling step of peeling the support from the photosensitive layer after the laminating step;
An exposure step of exposing a desired pattern to the photosensitive layer after the peeling step.   The pattern formation method according to claim 1, wherein the surface to be processed has irregularities. The substrate to be processed is a printed wiring board having printed wiring,
The pattern formation method according to claim 2, wherein the printed wiring forms irregularities on the surface to be processed.   The exposure amount in the exposure step is 1.1 to 3.0 times the exposure amount in the exposure step when the laminating step, the exposure step, and the peeling step are performed in this order. A pattern forming method according to any one of the above.   The pattern forming method according to claim 1, wherein the laminating step is performed using a vacuum roll laminator.   The pattern forming method according to claim 1, wherein the laminating step is performed using a vacuum press laminator.   The pattern forming method according to claim 1, further comprising a development step of developing the photosensitive layer after the exposure step.   The pattern formation method of Claim 7 including the permanent pattern formation process which forms a permanent pattern after the image development process.   The pattern forming method according to claim 1, wherein the photosensitive layer contains a polymerizable compound, a binder, and a photopolymerization initiator.   The pattern forming method according to claim 9, wherein the photosensitive layer further contains a thermal crosslinking agent.