TW201331713A - Photosensitive resin composition, photosensitive laminated body, flexible circuit board and method for forming permanent pattern - Google Patents

Abstract

The invention provides a photosensitive resin composition including: (A) a binder resin including an acid modified resin containing an ethylene unsaturated group, wherein the acid modified resin containing an ethylene unsaturated group includes a structure having an ability to restrain a radical polymerization at least one end of a main chain; (B) a radical polymerized compound; c a thermal crosslinking agent; and (D) a photoinitiator.

Description

Photosensitive resin composition, photosensitive laminate, flexible circuit board, and method for forming permanent pattern

The present invention relates to a photosensitive resin composition suitable as a solder resist material for a flexible substrate, and a photosensitive laminate, a flexible circuit board, and a permanent pattern forming method using the photosensitive resin composition.

In the prior art, a method of forming a permanent pattern such as a solder resist is known, for example, a method of forming a laminate by laminating a photosensitive resin composition using a roll coater or the like on a substrate such as a copper clad laminate having a permanent pattern formed thereon. The photosensitive layer in the laminate is exposed, and after the exposure, the photosensitive layer is developed to form a pattern, and then subjected to a curing treatment or the like to form a permanent pattern.

The photosensitive resin composition as described above has been proposed to contain a photosensitive resin composition containing (A) a binder polymer, (B) an organic filler, (C) a photopolymerizable compound, and (D) a photopolymerization initiator. (Patent Document 1).

The photosensitive resin composition slowly undergoes polymerization even during storage. Should cause the composition to gel. In order to prevent the gelation and to improve the storage stability, a polymerization inhibitor is usually added. However, if the amount of the polymerization inhibitor is increased in order to effectively suppress the gelation, the exposure sensitivity is lowered, and the performance as a photosensitive composition is lowered. decline. Therefore, it is desirable to more effectively suppress gelation of the composition without lowering the exposure sensitivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-169810

An object of the present invention is to provide a photosensitive resin composition which is excellent in both storage stability and exposure sensitivity, and is suitable for forming a solder resist. Further, an object of the present invention is to provide a photosensitive laminate, a flexible circuit board, and a method of forming a permanent pattern using the photosensitive resin composition.

The method for solving the above problems is as follows.

<1> A photosensitive resin composition comprising: (A) a binder resin comprising an acid-modified ethylenically unsaturated group-containing resin, wherein the acid-modified ethylenically unsaturated group-containing resin is at least 1 in a main chain One end contains a structure having a radical polymerization inhibiting ability; (B) a radical polymerizable compound; (C) a thermal crosslinking agent; and (D) a photopolymerization initiator.

(2) The photosensitive resin composition according to <1>, wherein the structure having the radical polymerization inhibiting ability is represented by the following general formula (PIa) or general formula (PIb):

In the formula (PIa) and the formula (PIb), R ^T1 represents a hydrogen atom or an aliphatic group; and R ^T2 represents a hydrogen atom, an aliphatic group or an oxygen radical.

<3> The photosensitive resin composition according to <1> or <2>, wherein the binder resin of the above (A) is an acid-modified polyurethane resin containing an ethylenically unsaturated group.

(4) The photosensitive resin composition according to <3>, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a partial structure represented by the following formula (U1):

In the formula (U1), L ^U1 represents an ethylenically unsaturated group and a divalent linking group which does not contain a carboxyl group.

<5> The photosensitive resin composition according to <4>, wherein L ^U1 in the above formula (U1) is -(CH ₂ CH ₂ O)n ^U1 CH ₂ CH ₂ -, -[CH ₂ CH (CH ₃ )O]n ^U1 -CH ₂ CH(CH ₃ )-, -(CH ₂ CH ₂ CH ₂ CH ₂ O)n ^U1 -CH ₂ CH ₂ CH ₂ CH ₂ -, the following general formula (LL1) The structure shown, the structure represented by the following general formula (LL2), the structure represented by the following general formula (LL3), or the structure represented by the following general formula (LL4):

Here, n ^U1 to n ^U4 , n and n′ each independently represent a number of 1 or more; and R ^LL1 , R ^LL2 and R each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group.

<6> The photosensitive resin composition according to <4> or <5>, wherein the molecular weight of L ^U1 in the above formula (U1) is from 400 to 8,000.

<7> The photosensitive resin composition according to <6>, wherein L ^U1 in the above formula (U1) has a molecular weight of 500 to 5,000.

The photosensitive resin composition according to any one of <3> to <7> wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has the following formula (UE1) Part of the structure represented by:

In the general formula (UE1), the L ^UE is a divalent linking group which does not contain -NHC(=O)O- or -OC(=O)NH- in the bond of the main chain, and has one on the side chain. a divalent linking group of an ethylenically unsaturated group.

<9> The photosensitive resin composition according to <8>, wherein the main chain in which the L ^UE in the above formula (UE1) is bonded to the oxygen atom of the two urethane bonds contains a divalent aliphatic group, An oxygen atom, a nitrogen atom, a sulfur atom or a combination thereof.

<10> The photosensitive resin composition according to <8> or <9>, wherein the above formula (UE1) is represented by the following formula (G1):

In the formula (G1), R ¹ to R ³ each independently represent a hydrogen atom or a substituent, A represents a divalent organic group, and X represents an oxygen atom, a sulfur atom or -N(R ¹² )-; wherein R ¹² represents A hydrogen atom or a substituent.

The photosensitive resin composition according to any one of <3> to <10> wherein the weight average molecular weight of the acid-modified ethylenically unsaturated group-containing polyurethane resin is 5,000~ 60,000, the acid value of the solid component is 10 mgKOH/g~120 mgKOH/g, and the ethylenic unsaturated group content is 0.05 mmol/g~1.2 mmol/g.

The photosensitive resin composition according to any one of <4> to <11> wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin is in the resin, and is HO. -L ^U1 -OH (L ^U1 represents an ethylenically unsaturated group and a divalent linking group which does not contain a carboxyl group), and has a partial structure represented by the above formula (U1) in an amount of 10% to 60% by mass of the solid content. .

<13> The photosensitive resin group according to any one of <3> to <12> The product wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin is at least one diisocyanate compound, at least one diol compound having an ethylenically unsaturated group and two hydroxyl groups, A resin obtained by reacting at least one diol compound of a carboxyl group and two hydroxyl groups with at least one diol compound having no ethylenically unsaturated group or a carboxyl group.

(1) The photosensitive resin composition according to <13>, wherein the diisocyanate compound has a 2,2-diphenylpropane type, a diphenylmethane type, a biphenyl type, a naphthalene type, a phenanthrene type or an anthracene type. Skeleton.

<15> A photosensitive layered body comprising a photosensitive layer comprising the photosensitive resin composition according to any one of <1> to <14> on a substrate.

<16> A flexible circuit board having a photosensitive layer containing the photosensitive resin composition according to any one of <1> to <14> on a substrate, and having the photosensitive layer lighted A resist pattern obtained by hardening is formed.

<17> The flexible circuit board according to <16>, wherein the substrate is a polyimide film.

<18> A method of forming a permanent pattern, comprising the step of exposing a photosensitive layer formed using the photosensitive resin composition according to any one of <1> to <14>.

The photosensitive resin composition of the present invention not only maintains good exposure sensitivity, but also has excellent storage stability and less development residue.

Since the photosensitive laminate of the present invention is formed by using the above-mentioned photosensitive resin composition, it not only maintains good exposure sensitivity but also has excellent storage stability. There are also fewer development residues.

Since the flexible circuit board of the present invention has less development residue, the pattern accuracy is high.

According to the permanent pattern forming method of the present invention, it is possible to form a pattern having improved pattern formation accuracy.

The above and other features and advantages of the present invention will be apparent from the description.

(Photosensitive resin composition)

The photosensitive resin composition of the present invention contains at least (A) a binder resin containing an acid-modified ethylenically unsaturated group-containing resin, and the acid-modified ethylenically unsaturated group-containing resin is at least one of the main chains. The terminal comprises a structure having a polymerization inhibiting ability; (B) a radical polymerizable compound; (C) a thermal crosslinking agent; and (D) a photopolymerization initiator; and further contains other components as needed.

<Binder resin>

The binder resin is a resin containing an acid-modified ethylenically unsaturated group-containing resin having a polymerization inhibiting structure to be described later at at least one terminal of the main chain. The above binder resin preferably contains all of the acid-modified ethylenically unsaturated group-containing resins, and more specifically, acid modification Polyethylenically unsaturated group-containing polyurethane resin, ethylenically unsaturated group-containing polycarboxylic acid resin, acid-modified ethylenically unsaturated group-containing epoxy resin, ethylenically unsaturated group and a resin of a carboxyl group, a polyimide precursor, and the like. Among the resins, the binder resin in the present invention is preferably an acid-modified ethylenically unsaturated group-containing polyurethane resin and an acid-modified ethylenically unsaturated group-containing epoxy resin, more preferably An acid-modified ethylenically unsaturated group-containing polyurethane resin.

Further, in the present invention, a vinyl group is used in the meaning of a vinyl group which may have a substituent.

"Acid-modified polyurethane resin containing ethylenically unsaturated group"

The acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose. In the present invention, an acid-modified polyurethane resin having an ethylenically unsaturated bond in a side chain is particularly preferred. In the present invention, the side chain means a chain which is branched from a chain constituting a main chain of a polyurethane resin or substituted on an atom constituting a main chain, and the side chain has an ethylenically unsaturated group. It means that an ethylenically unsaturated group is contained in such a side chain, or an ethylenically unsaturated group is directly substituted on the atom constituting the main chain. For example, a polyurethane resin obtained by only a reaction of a diol of HOCH ₂ CH=CHCH ₂ OH with OCN(CH ₂ ) ₆ NCO contains an ethylenically unsaturated group in the main chain.

In addition, the ethylenically unsaturated group means a group having a vinyl bond consumed by measurement of a bromine number or an iodine value, and is not a group indicating aromatic such as benzene. The ethylenically unsaturated group is preferably a vinyl group which may have a substituent.

The acid-modified resin refers to a resin having an acidic group in the resin. Acidic The group is preferably a phosphate group, a sulfonic acid group, a carboxylic acid group, a boronic acid group, a sulfonylamino group, a phenolic hydroxyl group or the like, and more preferably a carboxylic acid.

Hereinafter, the preferred molecular weight, acid value, ethylenically unsaturated group content and preferred content of the photosensitive resin composition of the acid-modified ethylenically unsaturated group-containing polyurethane resin used in the present invention will be described. .

Molecular Weight

The weight average molecular weight of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 5,000 to 60,000, more preferably 5,000 to 50,000. It is 5,000~40,000. When the weight average molecular weight is less than 5,000, when the photosensitive resin composition of the present invention is used for a photosensitive solder resist, there is a case where a sufficient low elastic modulus of the cured film at a high temperature cannot be obtained, and if it exceeds 60,000, There is a case where the coating suitability and the developability are deteriorated. In addition, when an inorganic filler is used, the inorganic filler is excellent in dispersibility, and is excellent in crack resistance and heat resistance, and is excellent in developability in a non-image portion of an alkaline developer.

Here, the weight average molecular weight can be, for example, a high performance gel permeation chromatography (High Efficiency GPC) apparatus (manufactured by Toyo Soda Co., Ltd., HLC-802A), and 0.5% by mass of tetrahydrofuran (THF). The solution was used as a sample solution. One column of TSKgel HZM-M was used to inject 200 μL of the sample, eluted with the above THF solution, and a refractive index detector or an ultraviolet (UV) detector was used at 25 ° C ( The detection wavelength was 254 nm). Then, according to the standard polystyrene The corrected molecular weight distribution curve of polystyrene was used to determine the weight average molecular weight.

Acid value

The acid value of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 10 mgKOH/g to 120 mgKOH/g, more preferably 15 MgKOH/g~110 mgKOH/g, particularly preferably 20 mgKOH/g~90 mgKOH/g. When the acid value is less than 10 mgKOH/g, the developability may be insufficient. When the acid value is more than 120 mgKOH/g, the development speed may be too high, and control of development may be difficult.

Here, the acid value can be measured, for example, in accordance with JIS K0070. Further, in the case where the sample is not dissolved, dioxane or tetrahydrofuran or the like is used as a solvent. Further, the acid value is a solid component acid value of the above resin.

"Ethylene Unsaturated Group Content"

The content of the ethylenically unsaturated group of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 0.05 mmol/g to 2.0 mmol/g. More preferably, it is 0.3 mmol/g to 1.9 mmol/g, more preferably 0.5 mmol/g to 1.8 mmol/g, and particularly preferably 0.7 mmol/g to 1.8 mmol/g, and particularly preferably 1.2 mmol/g or less. When the content of the ethylenically unsaturated group is less than 0.05 mmol/g, the heat resistance of the cured film may be poor, and if it exceeds 2.0 mmol/g, the folding resistance may be deteriorated.

Here, the content of the ethylenically unsaturated group can be determined, for example, by measuring the bromine number. The above bromine number can be measured, for example, in accordance with JIS K2605.

Further, here, the ethylenically unsaturated group equivalent is typically a vinyl equivalent, which is the number of grams of bromine (Br ₂ ) added by the above bromine number relative to 100 g of the measured resin (gBr ₂ / 100 g), converted to a value obtained by adding the molar number of bromine (Br ₂ ) per 1 g of the resin.

"Solid Concentration of Acid-Modified Ethylene Unsaturated Polyurethane Resin"

The content of the solid component in the solution of the polyurethane resin used in the present invention is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 10% by mass to 90% by mass, more preferably 20% by mass. 80% by mass, particularly preferably 30% by mass to 75% by mass, particularly preferably 40% by mass to 75% by mass, particularly preferably 45% by mass to 75% by mass.

When the content of the solid content is too small, the viscosity at the time of preparing the photosensitive resin is lowered, and the printing property may not be provided. If the content is too large, the viscosity is high, and the stirring may be poor during the synthesis and preparation of the photosensitive resin. The case of a photosensitive resin. When the content is in the above-mentioned particularly preferable range, it is advantageous in terms of both good printability and synthetic suitability.

Hereinafter, an acid-modified urethane resin having an ethylenically unsaturated bond in a preferred side chain of the present invention will be described.

The acid-modified urethane resin having an ethylenic unsaturated bond in the side chain is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include the following formula (1) to the formula in the side chain. (3) A resin of at least one of the functional groups represented.

In the formula (1), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group. Here, the monovalent organic group may, for example, be a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group or an aromatic group. Thio, amine, alkylamine, arylamine, decylamino, sulfonylamino, alkylsulfonyl or arylsulfonyl, alkylsulfinyl or arylsulfin Alkyl, alkoxycarbonyl, aryloxycarbonyl, decyl, decyloxy, carbamoyl, sulfonyl, hydroxy, decyl, cyano, nitro, carboxyl, sulfo, ureido, amine The acid group or the like may be further substituted by the substituents. Further, the same groups may be exemplified for each of the following groups or the monovalent organic group or the substituent in the respective formulas.

R ^{1 is} preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group from the viewpoint of high radical reactivity. Further, R ² and R ³ are each independently preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and may have a substitution. An aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamine group which may have a substituent, an alkyl group which may have a substituent a sulfonyl group, an arylsulfonyl group which may have a substituent, and more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or an alkyl group which may have a substituent, in terms of a high radical reactivity An aryl group having a substituent.

X represents an oxygen atom, a sulfur atom, or -N(R ¹² )-, and R ¹² represents a hydrogen atom or a monovalent organic group. R ^{12 is} preferably an alkyl group which may have a substituent, and more preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group in terms of a high radical reactivity.

Here, the substituent (the substituent which may be contained in the alkyl group which may have a substituent, etc.) which each of the above-mentioned groups may have is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include the above-mentioned monovalent organic group. Preferred group: halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amine group, alkylamino group, arylamine Base, mercaptoamine group, amine mercapto group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carboxyl group, sulfo group, nitro group, cyano group.

In the formula (2), R ⁴ to R ⁸ each independently represent a hydrogen atom or a monovalent organic group. R ⁴ to R ^{8 are} not particularly limited, and may be appropriately selected according to the purpose. Here, the monovalent organic group may be a group exemplified as R ¹ to R ³ in the above formula (1). R ⁴ to R ^{8 are} preferably a hydrogen atom, a halogen atom, an amine group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an arylamine group which may have a substituent, and a carboxyl group An alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, The alkylsulfonyl group having a substituent, the arylsulfonyl group which may have a substituent, and more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent in terms of a high radical reactivity An alkyl group, an aryl group which may have a substituent.

The substituent which each of the above groups may have is the same as the above formula (1). Further, Y represents an oxygen atom, a sulfur atom, or -N(R ¹² )-. R ¹² has the same meaning as in the case of R ¹² of the above formula (1), and preferred examples are also the same.

In the formula (3), R ⁹ to R ¹¹ each independently represent a hydrogen atom or a monovalent organic group. Here, the monovalent organic group may be a group exemplified as R ¹ to R ³ in the above formula (1). R ^{9 is} preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group from the viewpoint of high radical reactivity. R ¹⁰ and R ^{11 are} preferably a hydrogen atom, a halogen atom, an amine group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an arylamine group which may have a substituent, a carboxyl group, An alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, may have The alkylsulfonyl group of the substituent, the arylsulfonyl group which may have a substituent, and more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent in terms of a high radical reactivity An alkyl group, an aryl group which may have a substituent.

Here, examples of the substituent which each of the above groups may have are the same as those of the formula (1). Further, Z represents an oxygen atom, a sulfur atom, -N(R ¹³ )-, or a stretched phenyl group which may have a substituent. R ¹³ represents a hydrogen atom or a monovalent organic group. R ^{13 is} preferably an alkyl group which may have a substituent, and among them, a methyl group, an ethyl group, and an isopropyl group are more preferable in terms of a high radical reactivity.

Among the groups represented by the formula (1) to the formula (3), the group represented by the formula (1) is preferred, and in terms of the formability of the crosslinked cured film, a formula (preferably) is preferred. 1) A group in which R ¹ is a methyl group and R ² and R ³ are a hydrogen atom, a group in which R ¹ to R ³ in the formula (1) are each a hydrogen atom, and a group Z in the formula (3) More preferably, the styryl group of the phenyl group is a group in which R ¹ in the formula (1) is a methyl group and R ² and R ³ are a hydrogen atom, and R ¹ to R ³ in the formula (1) are both In the case of a group having a hydrogen atom, in terms of both the formability of the crosslinked cured film and the original preservability, it is particularly preferable that R ¹ in the formula (1) is a methyl group and R ² and R ³ are a hydrogen atom. Group. Here, X in the formula (1) is preferably an oxygen atom, and the ethylenically unsaturated group is preferably a methacryloxy group or an acryloxy group, and most preferably a methacryloxy group.

In order to introduce an ethylenically unsaturated group into a side chain, there are the following methods: (i) a method obtained by polymerization with a diisocyanate compound or a compound having an ethylenically unsaturated group in a diol compound; (ii) A carboxyl group-containing polyurethane obtained by reacting a compound having an epoxy group and an ethylenically unsaturated group in the molecule method.

Hereinafter, the polyurethane resin obtained by the method (i) is also referred to as a polyurethane resin (i), and the polyurethane resin obtained by the method of (ii) is also called It is a polyurethane resin (ii). Further, the polyurethane resin having an ethylenically unsaturated bond in the side chain includes both the polyurethane resin (i) and the polyurethane resin (ii).

In the present invention, the polyurethane resin (i) obtained by the method (i) is preferred.

-Polyurethane resin (i)-

The polyurethane resin is synthesized by reacting a diisocyanate compound with a diol compound (a compound having at least two hydroxyl groups), and the polyurethane resin (i) is a compound of the following formula (4) The structural unit represented by the reaction product of at least one of the diisocyanate compounds and the diol compound represented by the following general formula (5) is a basic skeleton of the polyurethane resin.

OCN-X ⁰ -NCO...General formula (4)

HO-Y ⁰ -OH... General formula (5)

In the general formulae (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

At least one of the diisocyanate compound represented by the above formula (4) or the diol compound represented by the above formula (5) has a group represented by the above formula (1) to formula (3). At least one of them is a polyurethane resin in which a group represented by the above formula (1) to formula (3) is introduced as a side chain. The reaction product of the diisocyanate compound and the diol compound. According to this method, the above-described general formula (1) to the general formula (3) can be more easily produced by substituting and introducing a desired side chain after the reaction with the polyurethane resin. The polyurethane resin of the indicated group.

The diisocyanate compound represented by the above formula (4) is not particularly limited and may be appropriately selected according to the purpose, and for example, one equivalent of a triisocyanate compound and a monofunctional alcohol or a monofunctional amine compound having an unsaturated group may be added. The product obtained by the reaction, and the like.

The triisocyanate compound is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include the compounds described in paragraphs [0034] to [0035] of JP-A-2005-250438.

The monofunctional alcohol or the monofunctional amine compound having an unsaturated group is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include those described in paragraphs [0037] to [0040] of JP-A-2005-250438. Compounds, etc.

The diisocyanate compound in the method of using a diisocyanate compound having an unsaturated group in a side chain is not particularly limited and may be appropriately selected according to the purpose, and can be obtained by allowing a triisocyanate compound and a monofunctional alcohol having an unsaturated group or a single The diisocyanate compound obtained by the addition reaction of the functional amine compound in an equivalent amount, for example, a compound having an unsaturated group in a side chain described in paragraphs [0042] to [0049] of JP-A-2005-250438, and the like. .

Improve compatibility with other components in the polymerizable composition, and improve protection The polyurethane resin (i) may also copolymerize a diisocyanate compound other than the above-described ethylenically unsaturated group-containing diisocyanate compound from the viewpoint of storage stability and the like.

The above-mentioned copolymerized diisocyanate compound is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a diisocyanate compound represented by the following formula (6).

OCN-L ¹ -NCO...General formula (6)

In the formula (6), L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If desired, L ¹ may have other functional groups that do not react with isocyanate groups, such as ester groups, urethane groups, guanamine groups, urea groups.

The diisocyanate compound represented by the above formula (6) is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include 2,4-tolylene diisocyanate and 2,4-toluene. Dimer of isocyanate, 2,6-toluene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1, An aromatic diisocyanate compound such as 5-naphthalene diisocyanate or 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate; An aliphatic diisocyanate compound such as trimethylhexamethylene diisocyanate, lysine diisocyanate or dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylene double (ring) An alicyclic diisocyanate compound such as hexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate or 1,3-(isocyanatemethyl)cyclohexane; 1,3-butanediol 1 molar and toluene A reaction product of a diol such as a cyanate ester 2 molar addition product with a diisocyanate, that is, a diisocyanate compound or the like.

The diisocyanate compound represented by the formula (4) or the formula (6) (particularly the diisocyanate compound represented by the formula (6)) can be used in combination of different kinds of compounds, but the aspect of folding endurance can be improved. In particular, at least one aromatic diisocyanate compound is preferred. The aromatic diisocyanate compound preferably has, for example, a bisphenol A type (hereinafter also referred to as 2,2-diphenylpropane type) or a bisphenol F type (hereinafter also referred to as diphenyl). a diisocyanate compound having a skeleton of a methane type, a biphenyl type, a naphthalene type, a phenanthrene type, or an anthracene type, more preferably a bisphenol A type or a bisphenol F type The backbone of the diisocyanate compound.

These various types of skeletons are represented by the following general formula.

In the above, R ^a and R ^b each independently represent a substituent, and the substituent is preferably an alkyl group having 2 to 5 carbon atoms. l ₁ and l ₂ independently represent integers from 0 to 4. l ₁ and l _{2 are} preferably 0 or 1. l ₃ represents an integer from 0 to 6. l ₄ represents an integer from 0 to 8. l _{3 is} preferably 0 to 2, and l _{4 is} preferably 0 or 2. When l ₁ to l ₄ are 2 or more, a plurality of R ^a and R ^b may be the same or different from each other.

The diisocyanate compound is more preferably an aromatic diisocyanate compound combined with an aliphatic diisocyanate compound from the viewpoint of suppressing warpage after curing to improve folding resistance. The aromatic diisocyanate compound is preferably, for example, a diisocyanate compound having a skeleton of a bisphenol A type, a bisphenol F type, a biphenyl type, a naphthalene type, a phenanthrene type, or a fluorene type, and more preferably a bisphenol A type or A diisocyanate compound of a bisphenol F type skeleton. The aliphatic diisocyanate compound is preferably, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate or diammonium acid diiso isocyanate. Cyanate ester, dimer acid diisocyanate, more preferably hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate.

The diol compound represented by the above formula (5) is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound.

Here, a method of introducing an ethylenically unsaturated group into a side chain of a polyurethane resin, in addition to the above method, preferably using a diol compound having an ethylenically unsaturated group in a side chain as a polyamine group A method of producing a raw material of an acid ester resin. The diol compound having an ethylenically unsaturated group in the side chain may be, for example, a compound commercially available as trimethylolpropane monoallyl ether, or may be a halogenated diol compound, a triol compound or an amine group. A compound which is easily produced by a reaction with a compound such as an alcohol compound, a compound such as an unsaturated group-containing carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol or a halogenated alkyl compound.

The diol compound having an ethylenically unsaturated group as described above is preferably a compound represented by the following formula (UE), and the polyurethane resin has a partial structure represented by the following formula (UE1).

General formula (UE) HO-L ^UE -OH

In the general formula (UE) and the general formula (UE1), the L ^UE is a divalent linking group which does not contain -NHC(=O)O- or -OC(=O)NH- in the bond of the main chain, and is represented by A divalent linking group having one ethylenically unsaturated group in the side chain.

The compound represented by the formula (UE) is preferably a compound represented by the following formula (UE-1) to (UE-6). Further, the compound represented by the following formula (UE-7) is preferably a compound other than the compound represented by the above formula (UE).

In the general formula (UE-1) to the formula (UE-7), E ¹ represents a single bond or a divalent linking group (divalent organic residue), and E ² represents a single bond or a divalent linkage other than -CH ₂ - base. A represents a divalent linking group. Q represents any one of the above formula (1) to formula (3). Examples of the divalent linking group in E ¹ and E ² include: -O-, -S-, -OCH(CH ₂ -Q)CH ₂ -, -CO ₂ -CH ₂ -, -OCH ₂ C (CH ₂ -Q) ₂ CH ₂ -, -O-CONHCH ₂ CH ₂ -, -OC(=O)-, -CONHCH ₂ CH ₂ -, -CH ₂ C(CH ₂ -Q) ₂ CH ₂ -, -CH ₂ -, -NHCONHCH ₂ CH ₂ -, -NHCH(CH ₂ -Q)CH ₂ -, -NCH(CH ₂ -Q)CH ₂ -, -NHCH ₂ C(CH ₂ -Q) ₂ CH ₂ -, -NH -CH(CH ₂ -Q)CH ₂ -, -C(=O)-, -CO ₂ -CH ₂ CH ₂ -, -CO ₂ -CH ₂ CH ₂ CH ₂ -, and the like. Further, here, Q represents a group of any one of the formulae (1) to (3).

Specific examples of the compound include the compounds described in paragraphs "0057" to "0060" of JP-A-2005-250438.

Among the compounds represented by the above formula (UE-1) to the formula (UE-7), a compound represented by the above formula (UE-1) to (UE-6) is preferred, and the above is particularly preferred. A compound represented by the formula (UE-6). Further, among the compounds represented by the formula (UE-6), a compound represented by the following formula (G) is particularly preferred. Further, the compound represented by the formula (G) has a partial structure represented by the following formula (G1) in the polyurethane resin.

In the general formula (G) and the general formula (G1), R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or -N ( R ¹² )-, R ¹² represents a hydrogen atom or a monovalent organic group.

Further, in the general formula (G), Formula (G1) in the R ¹ ~ R ³ and X in the general formula R (1) is ¹ ~ R ³ and X have the same meaning, further preferred embodiments are also the same.

The compound represented by the formula (G) includes the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438. Preferred in the present invention.

It is considered that by using a polyurethane resin derived from the diol compound represented by the above formula (G), it is possible to suppress excessive molecular motion of a polymer main chain caused by a sterically hindered secondary alcohol. The effect is to increase the film strength of the layer.

The polyurethane resin (i) of the present invention is acid-modified, and examples of the acid in the acid modification include a carboxylic acid and a sulfonic acid, and particularly preferably a carboxylic acid. In the case of synthesizing the polyurethane resin (i), it is preferred to carry out acid modification by using a diol compound having a carboxyl group. The diol compound having a carboxyl group includes, for example, the compounds represented by the following formulas (17) to (19).

In the formulae (17) to (19), R ¹⁵ may represent a hydrogen atom or may have a substituent (for example, a halogen atom such as a cyano group, a nitro group, a -F, -Cl, -Br or -I, -CONH). ₂ , -COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ , -OCONHR ¹⁶ (here, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl having 7 to 15 carbon atoms) The alkyl group, the aralkyl group, the aryl group, the alkoxy group, and the aryloxy group of each group are not particularly limited, and may be appropriately selected according to the purpose, and preferably have a hydrogen atom and a carbon number of 1. ~8 alkyl groups, 6 to 15 carbon atoms. In the above formulas (17) to (19), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different, and may have a single bond and may have a substituent (for example, an alkyl group or an aralkyl group is preferred). The divalent aliphatic or aromatic hydrocarbon group of the aryl group, the alkoxy group or the halogen atom is not particularly limited and may be appropriately selected according to the purpose, and is preferably an alkyl group or a carbon having 1 to 20 carbon atoms. The number of 6 to 15 extended aryl groups is more preferably an alkyl group having 1 to 8 carbon atoms. Further, if necessary, the above L ⁹ to L ¹¹ may have another functional group which does not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, a decyl group, a ureido group or an ether group. Further, a ring may be formed by two or three of the above R ¹⁵ , L ⁹ , L ¹⁰ and L ¹¹ .

In the above formula (18), Ar is not particularly limited as long as it is a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose, and is preferably an aromatic group having 6 to 15 carbon atoms. .

The diol compound having a carboxyl group represented by the above formulas (17) to (19) is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include 3,5-dihydroxybenzoic acid and 2,2-bis ( Hydroxymethyl)propionic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyl) Phenyl)acetic acid, 2,2- Bis(hydroxymethyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N,N-dihydroxyethylglycine, N,N-bis(2-hydroxyethyl) -3-carboxy-propanamide and the like. These compounds may be used alone or in combination of two or more.

The diol compound having a carboxyl group is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include a compound described in paragraph [0047] of JP-A-2007-2030.

Since such a carboxyl group is present, it is preferable to impart properties such as hydrogen bonding property and alkali solubility to the polyurethane resin. By introducing a carboxyl group in the above manner, the acid value can be adjusted to a preferred range in the present invention as described above.

Since such a carboxyl group is present, it is preferable to impart properties such as hydrogen bonding property and alkali solubility to the polyurethane resin. By introducing a carboxyl group in the above manner, the acid value can be adjusted to a preferred range in the present invention as described above.

Further, in the synthesis of a polyurethane resin having an ethylenically unsaturated bond in a side chain, in addition to the above diol compound, a compound in which a tetracarboxylic dianhydride is opened by a diol compound may be used in combination.

The compound which is a ring-opening of the tetracarboxylic dianhydride by the diol compound is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include paragraphs [0095] to [0101] of JP-A-2005-250438. The compound or the like described.

For example, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability, the polyurethane resin (i) may have two ethylenically unsaturated groups in the side chain. An alcohol compound or a diol compound containing a carboxyl group The external diol compound is copolymerized, and in the present invention, it is particularly preferred to copolymerize the above diol compound.

The diol compound is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a low molecular weight diol compound or a polyether diol compound as a polymer diol compound, a polyester diol compound, and a polycarbonate II. An alcohol compound, a polycarbonate compound of m-dihydroxybenzene, or the like.

The diol compound is represented by the following formula (U), and when it is incorporated as a polyurethane resin, it is represented by a partial structure represented by the following formula (U1).

General formula (U) HO-L ^U1 -OH

In the general formula (U) and the general formula (U1), L ^U1 represents an ethylenically unsaturated group and a divalent linking group which does not contain a carboxyl group.

L ^{U1 is} exemplified by an alkyl group, an extended aryl group, and a divalent heterocyclic group, and the alkylene group may include -O-, -OCOO-, a phenylene group, a carbon-carbon double bond in the alkyl chain. Carbon-carbon triple bond, -OCO-Z ¹ -COO- (Z ¹ represents an alkylene group, an extended alkenyl group, an extended aryl group).

In the diol compound represented by the formula (U), the low molecular weight diol compound is preferably a compound having a weight average molecular weight of less than 400, and examples thereof include those described in paragraph [0048] of JP-A-2007-2030. Compounds, etc.

In the present invention, a polymer diol compound is preferred, which will be described in detail below.

- polymer diol compound -

The polymer diol compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, and ethylene oxide/propylene oxide. a block copolymer or a random copolymer, a polytetramethylene glycol, a block copolymer of tetramethylene glycol and neopentyl glycol, or a polyether glycol such as a random copolymer; a polyol or a poly Ether diol with maleic anhydride, maleic acid, fumaric acid, methylene succinic anhydride, methylene succinic acid, adipic acid, terephthalic acid, isophthalic acid, etc. a condensate of a polybasic acid, that is, a polyester diol; obtained by a reaction of a diol or a bisphenol with a carbonate, or a reaction of phosgene with a diol or a bisphenol in the presence of a base. Polycarbonate such as caprolactone modified polymer diol such as caprolactone modified polytetramethylene glycol, polyolefin polymer diol, hydrogenated polybutadiene diol, etc. An olefin polymer diol, an anthrone ketone polymer diol, or the like. These compounds may be used alone or in combination of two or more.

Further, a preferred compound or partial structure in the present invention is that L ^U1 in the above formula (U) and formula (U1) is -(CH ₂ CH ₂ O)n ^U1 CH ₂ CH ₂ -, -[CH ₂ CH(CH ₃ )O]n ^U1 -CH ₂ CH(CH ₃ )-, -(CH ₂ CH ₂ CH ₂ CH ₂ O)n ^U1 -CH ₂ CH ₂ CH ₂ CH ₂ -, the following formula ( The structure represented by LL1), the structure represented by the following formula (LL2), the structure represented by the following formula (LL3), or the structure represented by the following formula (LL4).

Here, R ^LL1 , R ^LL2 and R each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group. n ^U1 ~ n ^U4 , n and n' each independently represent a number of 1 or more. n ^U1 to n ^U4 , n and n' are usually a number of 1000 or less, preferably 500 or less, more preferably 100 or less.

The divalent chain hydrocarbon group is preferably an alkyl group, an alkenyl group or an alkynyl group. The hydrocarbon groups may have a branch or a substituent. More preferably, the carbon number is 2-8, and examples thereof include an ethyl group, a trimethylene group, a propyl group, a tetramethylene group, a 2-methyl-tetramethylene group, a pentamethylene group, a hexamethylene group, and an octa An octamethylene, a 2-butenyl group, and a 2-butenyl group are preferred examples.

The divalent cyclic hydrocarbon group is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 6-membered ring. It may be a single ring or a condensed ring, preferably a single ring. It may be either an aromatic ring or an aliphatic ring. The aromatic ring may, for example, be a benzene ring or a naphthalene ring, and the aliphatic ring may, for example, be a cyclohexane ring or a bicyclo[2.2.2]octane ring.

Further, the compound represented by the formula (U) is also preferably a diol compound represented by the following formula (III-1) to formula (III-5).

The polyether diol compound is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include a compound described in paragraph [0068] to [0076] of JP-A-2005-250438.

The polyester diol compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include paragraphs [0077] to [0079] and [0083] to [0085] of JP-A-2005-250438. The compounds described in No. 1 to No. 8 and No. 13 to No. 18 in the middle.

The polycarbonate diol compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include the paragraphs [0080] to [0081] and [0084] of the Japanese Patent Laid-Open Publication No. 2005-250438. A compound or the like described in 9 to No. 12.

Further, in addition to the above diol compound, a diol compound having a substituent which does not react with an isocyanate group may be used in combination.

The diol compound having a substituent which does not react with an isocyanate group is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a Japanese patent. The compound or the like described in paragraph [0087] to paragraph [0088] of JP-A-2005-250438.

The weight average molecular weight of such a polymer diol compound is preferably from 400 to 8,000, more preferably from 500 to 5,000, still more preferably from 600 to 3,000, particularly preferably from 800 to 2,000. When the weight average molecular weight is less than 400, sufficient folding resistance may not be obtained. When the weight average molecular weight exceeds 8,000, the glass transition temperature (Tg) of the obtained polyurethane resin is excessively lowered, so that insulation reliability is lowered. Happening.

Here, the weight average molecular weight can be, for example, a high-efficiency GPC apparatus (manufactured by Toyo Soda Co., Ltd., HLC-802A), a 0.5 mass% THF solution as a sample solution, and a column using one TSKgel HZM-M, injecting 200 μL. The sample was eluted with the above THF solution, and measured at 25 ° C using a refractive index detector or a UV detector (detection wavelength: 254 nm).

The mass ratio of the partial structure represented by the above formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is preferably from 10% to 60%, more preferably from 15% to 60%. %, especially good is 20% to 55%, especially preferably 30% to 50%. When the mass ratio is less than 10%, the warpage suppression after hardening may become difficult. When the content exceeds 60%, the sensitivity of photocuring may be excessively lowered, and the resolution may be deteriorated.

Further, as the polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention, a resin having an unsaturated group at the terminal of the polymer and in the main chain is preferably used. A urethane resin having an ethylenically unsaturated bond in a photosensitive resin composition and a side chain by having an unsaturated group at a polymer terminal or a main chain Between the polyurethane resins having an ethylenically unsaturated bond in the side chain or in the side chain, the crosslinking reactivity is improved, and the strength of the photocured material is increased. Here, in terms of easiness of production of the crosslinking reaction, the unsaturated group is particularly preferably a carbon-carbon double bond.

The method of introducing an unsaturated group at the end of a polymer has the method shown below. In other words, in the step of synthesizing the polyaminourate resin having an ethylenically unsaturated bond in the side chain, the step of treating the residual isocyanate group at the end of the polymer with an alcohol or an amine is used as long as it is used. An alcohol having an unsaturated group, an amine or the like may be used. Specific examples of such a compound include the same compounds as those exemplified as the monofunctional alcohol or the monofunctional amine compound having an unsaturated group.

Further, from the viewpoint of easy control of the amount of introduction, increase in the amount of introduction, and improvement in crosslinking reaction efficiency, the unsaturated group is preferably introduced into the polymer side chain than the polymer terminal.

The ethylenically unsaturated bonding group to be introduced is not particularly limited, and may be appropriately selected according to the purpose, and is preferably a methacryl fluorenyl group, an acryl fluorenyl group or a styryl group in terms of crosslinkable cured film formability. More preferably, it is a methacryl fluorenyl group or an acryl fluorenyl group, and it is a methacryl fluorenyl group especially in terms of the formability of the cross-hardening film and the original storage property.

Further, the amount of the methyl methacrylate group introduced is not particularly limited and may be appropriately selected depending on the purpose, and the ethylenically unsaturated group content is preferably from 0.05 mmol/g to 2.0 mmol/g, more preferably from 0.3 mmol/g to 1.90. Methylene / g, especially preferably 0.5 mmol / g ~ 1.80 mmol / g, especially preferably 0.7 mmol / g ~ 1.8 mmol / g, of which the best is 1.2 Below mmol/g.

A method of introducing an unsaturated group into the main chain is a method of using a diol compound having an unsaturated group in the main chain direction for synthesizing a polyurethane resin. The diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include cis-2-butene-1,4-diol and trans-2-butene. Alkene-1,4-diol, polybutadiene diol, and the like.

The urethane resin contains a resin having a structure having a radical polymerization inhibiting ability (hereinafter also referred to as a polymerization inhibiting structure) at least one end of the main chain. Here, the polymerization inhibiting structure refers to a structure having a radical or a structure capable of generating a radical, which neutralizes other radicals which cause radical polymerization, and suppresses the progress of the radical polymerization reaction. .

The polymerization inhibiting structure is not particularly limited, and examples thereof include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, and tert-butyl catechol ( T-butyl catechol), pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine (phenothiazine), chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol (2,6-di-t-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 reactants, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al chelate a structure having a skeleton such as piperidine, preferably It is a structure represented by the following general formula (PIa) or general formula (PIb).

In the general formula (PIa) and the general formula (PIb), R ^T1 each independently represents a hydrogen atom or an aliphatic group. R ^T2 represents a hydrogen atom, an aliphatic group or an oxygen radical (-O.). Here, the plurality of R ^T1s may be the same or different from each other. Further, in the general formula (PIa), two R ^T1 groups bonded to the same carbon atom of the piperidine ring may be bonded to each other to form a ring.

The aliphatic group in the general formula (PIa) and the general formula (PIb) may be a straight chain, may have a branch, or may have a cyclic structure. The aliphatic group is preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms. More specifically, a methyl group, an ethyl group, an n-butyl group, an isopropyl group, a 2nd butyl group, a tert-butyl group, a 3rd pentyl group, a 3rd hexyl group, a 3rd octyl group, etc. are mentioned.

In the formula (PIa), R ^{T1 is} preferably a primary alkyl group or a hydrogen atom, and preferably all of R ^T1 is a primary alkyl group, particularly a methyl group.

In the formula (PIb), at least one of the two R ^T1 is preferably a secondary alkyl group or a tertiary alkyl group, more preferably a tertiary alkyl group. Further, it is preferred that two R ^T1 are each a tertiary alkyl group, and most preferably a third butyl group.

The method of introducing at least one polymerization inhibiting structure to the terminal of the main chain of the above-mentioned polyurethane resin is not particularly limited, and may be appropriately selected according to the purpose. For example, a hydroxy compound having a polymerization inhibiting structure or having a polymerization may be used. A method of suppressing a structure of an isocyanate compound as a raw material for producing a polyurethane resin. The introduction rate of the polymerization inhibiting structure at the end of the main chain of the above-mentioned polyurethane resin is not particularly limited, and a diisocyanate compound, a diol compound, and a polymerization inhibiting structure which are synthetic raw materials can be used as will be described later. The amount of the compound is appropriately adjusted to obtain a polyurethane resin which exerts a desired effect.

The hydroxy compound having a polymerization inhibiting structure may, for example, be a compound represented by the following formula (PIa') or the following formula (PIb').

In Formula (PIa ') and formula (PIb'), the same as R ^T1 and R ^T2, respectively, in the general formula (PIA) and formula (RIB) in the meaning of R ^T1 and R ^T2.

Specific examples of the compound represented by the above formula (PIa') and formula (PIb') include the following PI-1 to PI-4.

The polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention may be a known catalyst which is added with an activity corresponding to the respective reactivity in an aprotic solvent, and the above diisocyanate is used. The compound, the diol compound, and the above-described hydroxy compound having a polymerization inhibiting structure or an isocyanate compound having a polymerization inhibiting structure are synthesized by heating. The molar ratio (diisocyanate compound (M _a ): diol compound (M _b )) of the diisocyanate compound and the diol compound used for the synthesis is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 1:1.2. ~1.2:1. Further, the total number of moles (M _a+b ) of the diisocyanate and the diol compound used for the synthesis, the total molar amount of the hydroxy compound having a polymerization inhibiting structure for synthesis and/or the isocyanate compound having a polymerization inhibiting structure The ratio of the number (M _c ) (M _a+b : M _c ) is preferably from 50:1 to 2000:1, more preferably from 150:1 to 1500:1. Further, it can be synthesized in the form of not remaining an isocyanate group by treatment with an alcohol or an amine or the like after the above synthesis reaction.

The polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is particularly preferably a (meth) acrylate compound having two hydroxyl groups in the molecule as a diol compound. 2 hydroxy groups in the molecule The carboxylic acid of the group and the above polymer diol compound are obtained by reacting with a compound represented by the above formula (PIa') and/or the above formula (PIb').

-Polyurethane resin (ii)-

The polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule.

The polyurethane resin (ii) is a carboxyl group-containing polyurethane resin containing a diisocyanate or a carboxyl group-containing diol as an essential component, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule. A polyurethane resin obtained by carrying out the reaction. According to the purpose, as the diol component, a low molecular weight diol having a weight average molecular weight of 300 or less or a low molecular weight diol having a weight average molecular weight of 500 or more may be added as a copolymerization component.

When the polyurethane resin (ii) is used, since it is excellent in stable dispersibility, crack resistance, or impact resistance with an inorganic filler, heat resistance, moist heat resistance, adhesion, and mechanical properties, Improved electrical characteristics.

Further, the polyurethane resin (ii) is a diisocyanate of a divalent aliphatic or aromatic hydrocarbon which may have a substituent, and has a COOH group and two via a C atom and an N atom. The reactant of the OH group-containing carboxyl group-containing diol as an essential component may be obtained by reacting the obtained reactant with a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a -COO- bond. compound of.

Further, the above polyurethane resin (ii) is a compound of the following formula (I) At least one of the diisocyanate shown and the carboxyl group-containing diol compound represented by the formula (17) to formula (19) described in the above-mentioned polyurethane resin (i) is an essential component. And a reactant selected from at least one of the following general formulae (III-1) to (III-5) according to the purpose, or the obtained reactant and the following general formula (IV-) 1) A compound obtained by reacting a compound having an epoxy group and an ethylenically unsaturated group in the molecule represented by the formula (IV-16).

OCN-R ₁ -NCO Formula (I)

In the formula (I), R ₁ represents a divalent aliphatic or aromatic group which may have a substituent (for example, preferably an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom). hydrocarbon. If desired, R ₁ may have any other functional group that does not react with an isocyanate group, such as any of an ester group, a urethane group, a guanamine group, or a ureido group.

In the general formulae (III-1) to (III-3), R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ may be the same or different, and may represent a divalent aliphatic or aromatic hydrocarbon. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably an alkylene group having 2 to 20 carbon atoms or an extended aryl group having 6 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. An alkyl group or an alkyl group having 6 to 10 carbon atoms. R ₈ represents an alkyl group having 1 to 20 carbon atoms or an extended aryl group having 6 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms. Yan Fangji. Further, among R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups which do not react with an isocyanate group may be present, such as an ether group, a carbonyl group, an ester group, a cyano group, an alkene group or an aminocarboxylic acid. An ester group, a guanamine group, a ureido group, or a halogen atom or the like.

In the formula (III-4), R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group or a halogen atom. It is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a cyano group or a halogen atom, more preferably hydrogen. An atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Further, other functional groups which do not react with an isocyanate group may be present in R ₁₂ , such as an alkoxy group, a carbonyl group, an alkene group, an ester group or a halogen atom.

In the formula (III-5), R ₁₃ represents an aryl group or a cyano group, preferably an aryl group having 6 to 10 carbon atoms or a cyano group. m represents an integer from 2 to 4.

Further, in the above formula (III-1) to formula (III-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represent an integer of 2 or more, and preferably an integer of 2 to 100. In the above formula (III-5), n ₆ represents an integer of 0 or more, preferably 0 or an integer of 2 to 100.

In the general formulae (IV-1) to (IV-16), R ₁₄ represents a hydrogen atom or a methyl group, R ₁₅ represents an alkylene group having 1 to 10 carbon atoms, and R ₁₆ represents a hydrocarbon group having 1 to 10 carbon atoms. p represents an integer of 0 or 1 to 10.

Further, in the case where a carboxyl group-containing polyurethane is reacted with a compound having an epoxy group or an oxetane group in the molecule, it is a X, Y or Z and a polyurethane backbone. The linked partial structure has a structure of -CO ₂ - (an aliphatic group substituted with a hydroxyl group or a decyloxy group at the β-position or the γ-position) - (*). Here, the partial structure of the general formula (1) to the general formula (3) exists on the (*) side.

Further, the urethane resin (ii) may further copolymerize a low molecular weight diol having no carboxyl group as a fifth component, and the low molecular weight diol compound is represented by the above formula (III-1). A compound represented by the formula (III-5) or the above formula (LL3) and having a weight average molecular weight of 500 or less. The carboxyl group-free low molecular weight diol can be added as long as the alkali solubility does not decrease and the elastic modulus of the cured film can be kept sufficiently low.

The low molecular weight diol compound is, for example, a compound described in paragraph [0048] of JP-A-2007-2030.

The above urethane resin (ii) is particularly preferably an alkali-soluble photocrosslinkable polyurethane resin having an acid value of from 20 mgKOH/g to 120 mgKOH/g, and the alkali-soluble photocrosslinkable polyamine The urethane resin is an essential component of at least one of the diisocyanate represented by the above formula (I) and the carboxy group-containing diol selected from the above formulas (17) to (19), and According to the purpose, at least 1 of the polymer diols having a weight average molecular weight selected from the group consisting of the general formula (III-1) to the general formula (III-5) or the above general formula (LL3) in the range of 800 to 3,000 And a low molecular weight diol having a weight average molecular weight of 500 or less represented by the formula (III-1) to the formula (III-5) or the above formula (LL3) and reacting to obtain a reactant, Further, the reactant and the molecule represented by any one of the formulae (IV-1) to (IV-16) have one epoxy. The base is obtained by reacting at least one compound of (meth)acryl (acryl) acryl.

Further, in the above urethane resin (ii), it is also preferred to use the diol compound represented by the formula (U) described in the above urethane resin (i) instead of the above. a compound represented by the formula (III-1) to the formula (III-5) or the above formula (LL3), or a combination of the above formula (III-1) to formula (III-5) or the above formula (LL3) The compound represented by the formula and the diol compound represented by the formula (U) described in the above polyurethane resin, the acid-modified ethylenically unsaturated group-containing polyurethane The mass ratio of the partial structure represented by the above formula (U1) in the resin is the same as in the case of the above-mentioned polyurethane resin (i).

These polymer compounds may be used alone or in combination of two or more.

The polyurethane resin (ii) contains a resin having a polymerization inhibiting structure at at least one end of the main chain. In this case, the method of introducing the polymerization inhibiting structure or the preferred structure thereof is the same as that described in the polyurethane resin (i).

- a method for synthesizing a polyurethane resin (ii) obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule -

As a method for synthesizing the above-mentioned polyurethane resin (ii), the above-mentioned diisocyanate compound and diol compound can be added to a non-protic solvent by adding a known catalyst having an activity corresponding to each reactivity. Further, the above-described hydroxy compound having a polymerization inhibiting structure or an isocyanate compound having a polymerization inhibiting structure is synthesized by heating. The moie ratio (diisocyanate compound (M _{a '} ): diol compound (M _{b '} )) of the diisocyanate compound and the diol compound to be used is preferably 1: 1.2 to 1.2:1. Further, the total number of moles (M _{a' + b'} ) of the diisocyanate and the diol compound used for synthesis, the total amount of the hydroxy compound having a polymerization inhibiting structure for synthesis and/or the isocyanate compound having a polymerization inhibiting structure The ratio of the molar number (M _{c '} ) (M _{a' + b'} : M _{c '} ) is preferably from 50:1 to 2000:1, more preferably from 150:1 to 1500:1. When the isocyanate group remains at the terminal of the polymer, it is synthesized by treatment with an alcohol or an amine, and finally does not remain as an isocyanate group.

"Content of acid-modified ethylenically unsaturated group-containing polyurethane resin"

The acid-modified ethylenically unsaturated group-containing polyurethane resin (i) and the polyurethane resin (ii) used in the present invention may also be used in combination with the specific polyaminocarboxylic acid. An alkali-soluble polymer of a polyurethane resin having a different structure of an ester resin. For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain may be a combination of an aromatic group-containing polyurethane resin in a main chain and/or a side chain.

The content of the polyurethane resin used in the present invention is not particularly limited as long as it is contained in the solid content (nonvolatile content) of the photosensitive resin composition, and may be appropriately selected depending on the purpose, and is preferably 5% by mass to 80% by mass. %, more preferably 10% by mass to 75% by mass, particularly preferably 10% by mass to 70% by mass, particularly preferably 10% by mass to 60% by mass, particularly preferably 10% by mass to 50% by mass, particularly preferably 20% The mass% is 50% by mass, and particularly preferably 30% by mass to 50% by mass.

When the content is too small, the folding endurance may not be maintained well, and if it is too large, the heat resistance may be deteriorated. When the content is in the above-mentioned particularly preferable range, it is advantageous in that it has good folding endurance and heat resistance.

<Flame retardant>

The photosensitive resin composition of the present invention preferably contains one or more kinds of flame retardants.

Examples of the flame retardant include a phosphorus compound, or a brominated compound such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A or hexabromocyclododecane, and chlorination. A chlorinated compound or the like such as chlorinated paraffin is preferably a phosphorus-containing flame retardant.

"phosphorus-containing flame retardant"

Examples of the phosphorus-containing flame retardant include a condensed phosphoric acid compound, a melamine polyphosphate salt, a phosphazene compound, and an organic phosphinic acid metal salt. These compounds may be used alone or in combination of two or more.

The condensed phosphoric acid compound is, for example, resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A double A commercially available product can be used as the diphenyl phosphate, and examples of the commercially available product include CR-733S, CR-741, CR-747, PX-200 (above, manufactured by Daiha Chemical Co., Ltd.), and FP. -600, FP-700 (above, manufactured by Adeka Co., Ltd.), Reofos RDP, Reofos BAPP (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and the like.

The melamine polyphosphate salt is, for example, a compound represented by the following formula, and n represents a number of 1 or more. Commercial products can be used. Examples of the commercially available product include AP750, AP760, and OP1312 (the above is manufactured by Clariant Japan Co., Ltd.). FP-2100J, FP-2200 (above manufactured by Adico Co., Ltd.), Hishigard 6ME (manufactured by Nippon Chemical Industry Co., Ltd.), FCP-770 (manufactured by Suzuki Chemical Co., Ltd.), and the like.

The phosphazene compound is, for example, a compound represented by the following formula, and R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a commercially available product can be used. As a commercial item, SPS-100 (made by Otsuka Chemical Co., Ltd.), etc. are mentioned, for example.

The organic phosphinic acid metal salt is, for example, a compound represented by the following formula: A ^P and B ^P each independently represent an alkyl group or an aryl group, and M is selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, and At least one of Zn, Fe, Zr, Ce, Bi, Sr, Mn, Ni, and Na, and m represents an integer of 1 to 4. Here, M is preferably Al. Further, A ^P and B ^{P are} preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group. A commercially available product can be used as the organic phosphinic acid metal salt, and examples of the commercially available product include OP-935 (manufactured by Clariant, Japan).

In the present invention, a metal phosphinic acid metal salt is particularly preferred.

The content of the flame retardant in the solid content (nonvolatile content) of the photosensitive resin composition is preferably 5% by mass to 30% by mass, and more preferably 10% by mass to 20% by mass. When it is in the above preferred range, the composition is excellent in resolution, and the flame retardancy, folding endurance, and insulation reliability of the cured film can be kept 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 may be appropriately selected according to the purpose. For example, it is preferably an initiator which is sensitive to light from an ultraviolet region to visible light. It may be an active agent which generates a living radical by a certain action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the photopolymerization initiator preferably contains at least one species at a wavelength of about It is a component having a molecular absorption coefficient of at least about 50 in the range of 300 nm to 800 nm. The above wavelength is more preferably from 330 nm to 500 nm.

The above photopolymerization initiator is preferably a neutral photopolymerization initiator. In addition, other photopolymerization initiators may be included as needed.

The above-mentioned neutral photopolymerization initiator is not particularly limited and may be appropriately selected according to the purpose, and is preferably a compound having at least an aromatic group, more preferably (bis) fluorenylphosphine oxide or an ester thereof or acetophenone. (acetophenone) compound, benzophenone compound, benzoin ether compound, ketal derivative compound, thioxanthone compound. Two or more kinds of the above-mentioned neutral photopolymerization initiators may be used in combination.

Examples of the photopolymerization initiator include (bis) fluorenylphosphine oxide or an ester thereof, an acetophenone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, and a thioxanthone compound. , anthracene derivatives, organic peroxides, thio compounds, and the like. Among these compounds, an anthracene derivative, a (bis) fluorenylphosphine oxide or an ester thereof is preferred from the viewpoints of sensitivity and storage stability of the photosensitive layer, and adhesion between the photosensitive layer and the substrate for forming a printed wiring board. An acetophenone-based compound, a benzophenone-based compound, a benzoin ether-based compound, a ketal derivative compound, and a thioxanthone compound.

The (bis) fluorenylphosphine oxide, the acetophenone-based compound, the benzophenone-based compound, the benzoin-ether compound, the ketal derivative compound, and the thioxanthone compound may, for example, be Japanese Patent Publication No. 2010 (bis) fluorenylphosphine oxide, acetophenone-based compound, and diphenyl benzoyl group described in paragraph [0042] of the '256 publication A ketone compound, a benzoin ether compound, a ketal derivative compound, a thioxanthone compound, or the like.

The anthracene derivative described in paragraphs [0043] to [0059] of JP-A-2010-256399, for example, may be mentioned.

The photopolymerization initiator may be used singly or in combination of two or more.

The content of the photopolymerization initiator in the solid content of the photosensitive resin composition is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass. %, particularly preferably from 0.5% by mass to 15% by mass.

<thermal crosslinking agent>

The thermal crosslinking agent to be used in the present invention is not particularly limited, and can be appropriately selected according to the purpose, and the film strength after curing of the photosensitive layer formed using the photosensitive resin composition can be improved, and the developability can be prevented. In the range which causes an adverse effect, for example, a compound containing an epoxy compound (for example, an epoxy compound having at least 2 ethylene oxide groups in one molecule) and oxygen having at least 2 oxetanyl groups in one molecule are used. The heterocyclic butane compound may, for example, be an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, or an oxetanyl group as described in JP-A-2007-47729. An oxetane compound, a polyisocyanate compound, a compound obtained by reacting a block agent with an isocyanate group of a polyisocyanate or a derivative thereof, or the like.

Further, the above thermal crosslinking agent may use a melamine derivative. Examples of the melamine derivative include methylol melamine and alkylated methylol melamine (will A compound in which a methylol group is etherified with a methyl group, an ethyl group, a butyl group or the like). These compounds may be used alone or in combination of two or more. Among these compounds, the storage stability is good, and the surface hardness of the photosensitive layer or the film strength of the cured film itself is effective, and it is preferably alkylated methylol melamine, particularly preferably hexamethylated. Hydroxymethyl melamine.

The content of the thermal crosslinking agent in the solid content of the photosensitive resin composition is preferably from 1% by mass to 50% by mass, and more preferably from 3% by mass to 30% by mass. When the content is 1% by mass or more, the film strength of the cured film is improved, and when it is 50% by mass or less, the developability and the exposure sensitivity are improved.

The epoxy compound may, for example, be an epoxy compound having at least two ethylene oxide groups in one molecule, or an epoxy compound containing at least two epoxy groups having an alkyl group at the β position in at least one molecule.

Examples of the epoxy compound having at least two ethylene oxide groups in the above-mentioned one molecule include a bisphenol F type epoxy resin (Epotohto YDF-170, manufactured by Tohto Kasei Co., Ltd.), and a bixylenol type. Or a biphenol type epoxy resin ("YX4000, manufactured by Nippon Epoxy Co., Ltd.") or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton or the like ("TEPIC, Nissan Chemical Industry Co., Ltd." Manufacture, "Araldite PT810, manufactured by Ciba Specialty Chemicals", bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenation double Phenolic A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated epoxy resin (such as low brominated epoxy resin, high halogen epoxy resin) ,bromine a phenol novolak type epoxy resin, etc., an allyl-containing bisphenol A type epoxy resin, a trisphenol methane type epoxy resin, a diphenyl dimethanol type epoxy resin, a phenol biphenyl type epoxy resin, Dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H, manufactured by Dainippon Ink Chemical Industry Co., Ltd."), epoxypropylamine type epoxy resin (diaminodiphenylmethane type) Epoxy resin, diepoxypropyl aniline, triepoxypropylaminophenol, etc., epoxy propyl ester type epoxy resin (diglycidyl phthalate, diglycidyl adipate) , hexahydrophthalic acid diglycidyl phthalate, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4-epoxycyclohexyl Formic acid-3',4'-epoxycyclohexylmethyl ester, bis(3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, "GT-300, GT- 400, ZEHPE3150, manufactured by Daicel Chemical Industries Co., Ltd., bismuth imine type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type ring Oxygen resin, tetraphenylolethane type epoxy resin, butyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthyl group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available product "ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd. "HP-4032, EXA-4750, EXA-4700, manufactured by Dainippon Ink Chemical Industry Co., Ltd.", etc., by addition of a phenol compound to a diene compound such as divinylbenzene or dicyclopentadiene a compound obtained by reacting a polyphenol compound with epichlorohydrin, a compound obtained by epoxidizing a ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like, having a thread Phosphorus-containing knot Epoxy resin, epoxy resin with ring-shaped phosphorus structure, α-methylstilbene type liquid crystal epoxy resin, diphenylmethyloxy phenyl liquid crystal epoxy resin, even Nitrophenyl phenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine type epoxy resin, methacrylic acid Glycidyl ester copolymerized epoxy resin ("CP-50S, CP-50M, manufactured by Nippon Oil & Fats Co., Ltd."), copolymerization of cyclohexylmethyleneimine and glycidyl methacrylate Epoxy resin, bis(goxypropyloxyphenyl)fluorene type epoxy resin, bis(goxypropyloxyphenyl)adamantane type epoxy resin, and the like. These epoxy compounds may be used alone or in combination of two or more.

Further, in addition to the above epoxy compound having at least two ethylene oxide groups in one molecule, an epoxy compound containing at least one epoxy group having an alkyl group at the β-position in at least one molecule may be used, and preferably β is used. A compound having an alkyl-substituted epoxy group (more specifically, a β-alkyl-substituted epoxypropyl group, etc.).

The epoxy compound containing at least an epoxy group having an alkyl group at the β-position may be one or more epoxy groups contained in one molecule, and the epoxy group may be substituted with a β-alkyl group, or may be at least one. The epoxy group is a β-alkyl substituted epoxypropyl group.

The oxetane compound may, for example, be an oxetane compound having at least two oxetanyl groups in one molecule.

Specifically, for example, in addition to 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-oxetanyl) Oxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, methacrylic acid (3- Methyl-3-oxetanyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or a polyfunctional oxetane such as an oligomer or copolymer thereof Other than the class, a compound having an oxetane group, a novolac resin, a poly(p-hydroxystyrene), a cardo type bisphenol, a calixarene, a resorcinol calixarene ( An ether compound such as a resin having a hydroxyl group such as a sulphite or a silsesquioxane, and an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned. Copolymers, etc.

Further, as the polyisocyanate compound, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound can be substituted by an aliphatic, cyclic aliphatic or aromatic group containing at least two isocyanate groups. Derived from aliphatic compounds. Specific examples thereof include difunctional isocyanates (for example, a mixture of 1,3-phenyldiisocyanate and 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate, 1,3- Benzyl diisocyanate and 1,4- phenyldimethyl diisocyanate, bis(4-isocyanate-phenyl)methane, bis(4-isocyanate cyclohexyl)methane, isophorone diisocyanate, hexamethylene a difunctional isocyanate, a polyfunctional alcohol such as trimethylolpropane, pentaerythritol, glycerin or the like; an alkylene oxide adduct of the polyfunctional alcohol and the above-mentioned difunctional An adduct of an isocyanate; a cyclic trimer such as hexamethylene diisocyanate or hexamethylene-1,6-diisocyanate or a derivative thereof.

a compound obtained by reacting a block agent with the above polyisocyanate compound The isocyanate group block in the compound obtained by reacting the block agent with the isocyanate group of the polyisocyanate and the derivative thereof may, for example, be an alcohol (for example, isopropanol, tert-butanol, etc.) or a hydrazine. Amines (such as ε-caprolactam, etc.), phenols (such as phenol, cresol, p-tert-butylphenol, p-tert-butylphenol, p-second amyl phenol, p-octyl phenol, palladium a phenol (etc.), a heterocyclic hydroxy compound (for example, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), an active methylene compound (for example, dialkyl malonate, methyl ethyl ketoxime) ), etidinylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). In addition to the above-mentioned compounds, a compound having at least one polymerizable double bond and at least one block isocyanate group in the molecule described in JP-A-H06-295060 can be used.

Examples of the melamine derivative include methylol melamine and alkylated methylol melamine (a compound obtained by etherifying a methylol group with a methyl group, an ethyl group, a butyl group or the like). These compounds may be used alone or in combination of two or more. Among these compounds, the storage stability is good, and the surface hardness of the photosensitive layer or the film strength of the cured film itself is effective, and it is preferably alkylated methylol melamine, particularly preferably hexamethylated. Hydroxymethyl melamine.

<Thermal hardening catalyst>

The photosensitive resin composition of the present invention may contain a thermosetting catalyst. As the thermosetting catalyst, for example, the catalyst described in paragraph [0093] of JP-A-2008-250074 can be used.

<Free radical polymerizable compound>

The radically polymerizable compound used in the present invention is not particularly limited, and may be appropriately selected according to the purpose, and is preferably a compound containing one or more functional groups having an ethylenically unsaturated group.

Examples of the functional group having an ethylenically unsaturated group include (meth)acryloyl, (meth)acrylamide, vinylphenyl, vinyl ester, vinyl ether, and alkene. A propyl ether group, an allyl ester group or the like.

The compound containing one or more functional groups having an ethylenically unsaturated group is not particularly limited and may be appropriately selected according to the purpose, and is preferably selected from monomers having (meth)acryloyl (meth)acryl. At least one of them.

The monomer having a (meth) acrylonitrile group is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate. Monofunctional acrylate or monofunctional methacrylate such as phenoxyethyl (meth) acrylate; polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, dicyclopentane Dimethylol di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylic acid Ester, pentaerythritol tetra(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane diol di(meth) acrylate , trimethylolpropane tris(propylene oxypropyl)ether, tris(propylene decyloxyethyl)isocyanurate, tris(propylene decyloxyethyl) cyanurate, glycerol tris(A) Acrylate; making ethylene oxide or propylene oxide with polyfunctional alcohols such as trimethylolpropane, glycerin, bisphenol a compound obtained by addition of (meth) acrylate after addition reaction; epoxy resin and (A) The reaction product of acrylic acid, that is, a polyfunctional acrylate such as an epoxy acrylate or a methacrylate. Among these compounds, more preferred are trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, Polycyclic pentane dimethylol di(meth) acrylate, tricyclodecane dimethanol (meth) acrylate, epoxy resin and (meth) acrylate Acrylate or methacrylate.

The radical polymerizable compound is particularly preferably a polyfunctional acrylate such as a compound having two or more acryloxy groups or methacryloxy groups or a reaction product of an epoxy resin and (meth)acrylic acid, that is, an epoxy acrylate. Methacrylate.

The content of the radical polymerizable compound in the solid content of the photosensitive resin composition is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass. %. When the content is 5% by mass or more, the developability and the exposure sensitivity are good, and when the content is 50% by mass or less, the adhesion of the photosensitive layer can be prevented from becoming too strong.

<Inorganic Filler>

The photosensitive resin composition of the present invention may contain an inorganic filler. By containing an inorganic filler, not only the viscosity of the composition can be maintained well, but also the dripping at the time of coating can be prevented.

Examples of the inorganic filler include kaolin, barium sulfate, barium titanate, cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and the like. For the commercial product of the above-mentioned barium sulfate, for example, B-30 (manufactured by Nippon Chemical Industry Co., Ltd.) Made) and so on.

Among these inorganic fillers, a compound having a ruthenium atom such as ruthenium dioxide (a compound constituting ruthenium in an atom such as ruthenium dioxide or talc), ruthenium sulfate, aluminum hydroxide, or more preferably a compound having a ruthenium atom is preferable. , especially good for cerium oxide.

The average particle diameter of the inorganic filler is not particularly limited and may be appropriately selected according to the purpose, and is 5 μm or less, preferably 1 μm or less, and more preferably 0.5 μm or less. When the average particle diameter is 5 μm or more, the resolution may be deteriorated due to light scattering.

The content of the inorganic filler in the solid content of the photosensitive resin composition of the present invention is preferably from 1% by mass to 30% by mass, and more preferably from 5% by mass to 20% by mass.

<Other ingredients>

The other components are not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a filler, a thermal polymerization inhibitor, a plasticizer, a colorant (coloring pigment or dye), and the like, and may be used in combination with the surface of the substrate. Promoters and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.).

By appropriately containing these components, properties such as stability and film physical properties of the intended photosensitive resin composition can be adjusted.

Examples of the plasticizer include paragraphs [0103] to [0104] of JP-A-2008-250074.

Examples of the coloring agent include paragraphs [0105] to [0106] of JP-A-2008-250074.

Examples of the adhesion promoter include paragraphs [0107] to [0109] of JP-A-2008-250074.

The photosensitive resin composition of the present invention usually contains an organic solvent. The solvent is not particularly limited and may be appropriately selected depending on the purpose.

(photosensitive laminate)

The photosensitive laminate of the present invention has at least a base material and a photosensitive layer on the base material, and further laminates other layers as necessary.

The photosensitive layer is a layer containing a layer derived from the photosensitive resin composition of the present invention.

The photosensitive layer can be directly coated with the photosensitive resin composition of the present invention by, for example, a spin coater, a slit coater, a roll coater, a die coater, a curtain coater, or the like. The substrate was dried and set.

The drying conditions are also different depending on the components, the type of the solvent, the ratio of use, and the like, and are usually from about 30 seconds to about 60 minutes at a temperature of from 60 ° C to 110 ° C.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and particularly preferably 4 μm to 30 μm.

<Substrate>

The substrate is not particularly limited and may be appropriately selected according to the purpose, and may be arbitrarily selected from a substrate having a high surface smoothness to a substrate having a surface having a convex or concave surface, and preferably a plate-shaped substrate, that is, a substrate. . Specifically, a known substrate for producing a printed wiring board (printed substrate), a glass plate (such as a soda glass plate), and the like can be used. In the present invention, a resin film, paper, metal plate or the like is particularly preferably a metal or a polyimide film having a metal wiring formed thereon.

The photosensitive laminate of the present invention can be widely used for the formation of high-definition permanent patterns in the field of electronic materials, and can be suitably used for permanent pattern formation of printed substrates, particularly flexible wiring boards.

(Formation method of permanent pattern)

The method of forming the permanent pattern of the present invention includes at least an exposure step, and further includes other steps as needed.

<Exposure step>

The exposure step is not particularly limited as long as it is a step of exposing the photosensitive layer formed by the photosensitive resin composition of the present invention, and may be appropriately selected according to the purpose, and examples thereof include the photosensitive laminate of the present invention. The photosensitive layer is subjected to exposure steps and the like.

The above exposure is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include digital exposure, analog exposure, and the like.

<Other steps>

The other steps described above are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a surface treatment step of a substrate, a development step, a hardening treatment step, a post-exposure step, and the like.

- development step -

The above development step is a step of removing the unexposed portion of the photosensitive layer Step.

The method of removing the exposed portion is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a method of removing with a developing solution.

The developing solution is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include a developing solution described in paragraphs [0171] to [0173] of JP-A-2008-250074.

- Hardening treatment steps -

The hardening treatment step is a step of hardening the photosensitive layer in the formed pattern after performing the above-described development step.

The hardening treatment step is not particularly limited, and may be appropriately selected depending on the purpose. For example, a full exposure treatment, a total heat treatment, or the like is suitably exemplified.

The above-described overall exposure treatment and the method of the above-described overall heat treatment are not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include the methods described in paragraphs [0176] to [0177] of JP-A-2008-250074. Wait.

In the case where the method of forming the permanent pattern is a permanent pattern forming method of forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern forming method can be utilized on a printed substrate, particularly the present invention. In the middle, a permanent pattern is formed on the flexible wiring board, and further soldering is performed as follows.

That is, by the above development, a hardened layer as the permanent pattern is formed, and a metal layer is exposed on the surface of the printed substrate. Gold plating is performed on a portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Next, a semiconductor or a component or the like is mounted on the portion where the soldering has been performed. At this time, the permanent pattern of the hardened layer is The function as a protective film or an insulating film (interlayer insulating film), a solder resist, particularly a flexible solder resist, prevents an external impact or an adjacent electrode from being turned on.

(flexible circuit board)

The flexible circuit board of the present invention has at least a base body and a permanent pattern formed by the above-described permanent pattern forming method, and further has another member appropriately selected as needed.

The other member is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a build-up substrate in which an insulating layer is further provided between the substrate and the permanent pattern.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. Further, "parts" in the examples mean "parts by mass".

Further, the acid value, the weight average molecular weight, and the ethylenically unsaturated group content in the production examples were measured by the following methods.

Acid value

The above acid value is measured in accordance with JIS K0070. Among them, in the case where the sample is not dissolved, dioxane or tetrahydrofuran or the like is used as a solvent.

<weight average molecular weight>

The above weight average molecular weight was measured by a high-efficiency GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.). That is, a 0.5% by mass solution of THF (tetrahydrofuran) was used as a sample solution, and two TSKgel GMH6 columns were used for the column. 200 μL of the sample was eluted with the above THF solution, and the measurement was carried out at 25 ° C using a refractive index detector. Then, the weight average molecular weight was determined from the molecular weight distribution curve corrected by standard polystyrene.

<Ethylene unsaturation group content>

The ethylenically unsaturated group content was determined by measuring the bromine number in accordance with JIS K2605.

<Preparation example>

The acid-modified ethylenically unsaturated group-containing resin S-1 shown below, the acid-modified ethylenically unsaturated group-containing resin P-1, and the acid-modified ethylenically unsaturated group were prepared in the following manner. The base resin P-4 was used as a binder resin (the value in the formula is % by mol).

Preparation Example 1 Synthesis of acid-modified ethylenically unsaturated group-containing resin S-1

2,2-bis(hydroxymethyl)propionic acid (DMPA) 60.00 g (0.447 mol), glycerol monomethacrylate (GLM) in a 2 L three-neck round bottom flask equipped with a condenser and a stirrer 62.87 g (0.392 mol), poly(propylene glycol) 210.21 g and p-benzoquinone 1.65 g were dissolved in 294 g of cyclohexanone. 4,4-diphenylmethane diisocyanate (MDI) 131.39 g (0.525 mol), hexamethylene diisocyanate (HDI) 88.30 g (0.525 mol), cyclohexanone 239 g and as a catalyst were added thereto. 1.76 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was heated and stirred at 60 ° C for 5 hours. Then, it was diluted with 13 mL of methanol, and stirred for 30 minutes to obtain 1100 g of an acid-modified vinyl group-containing polyurethane adhesive S-1 solution (solid content: 50% by mass). The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a weight average molecular weight of 20,000, a solid content acid value of 46 mgKOH/g, and an ethylenically unsaturated group content of 0.71 mmol/g.

Preparation Example 2 Synthesis of Acid-Modified Ethylenic Unsaturated Resin P-1 having a polymerization inhibiting structure

In a 2 L three-neck round bottom flask equipped with a condenser and a stirrer, 2,2-bis(hydroxymethyl)propionic acid (DMPA) 60.00 g (0.447 mol), glycerol monomethacrylate (GLM) 62.87 g (0.392 mol), poly(propylene glycol) 210.21 g, and 4- Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo 1.10 g was dissolved in 294 g of cyclohexanone. 4,4-diphenylmethane diisocyanate (MDI) 131.39 g (0.525 mol), hexamethylene diisocyanate (HDI) 88.30 g (0.525 mol), cyclohexanone 239 g and as a catalyst were added thereto. 1.76 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was heated and stirred at 60 ° C for 5 hours. Then, it was diluted with 13 mL of methanol, and stirred for 30 minutes to obtain 1,100 g of an acid-modified vinyl group-containing polyurethane binder P-1 solution (solid content: 50% by mass). The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a weight average molecular weight of 20,000, a solid content acid value of 46 mgKOH/g, and an ethylenically unsaturated group content of 0.71 mmol/g.

Preparation Example 3 Synthesis of Acid-Modified Ethylenic Unsaturated Resin P-2 having a polymerization inhibiting structure

2,2-bis(hydroxymethyl)propionic acid (DMPA) 60.00 g (0.447 mol), glycerol monomethacrylate (GLM) in a 2 L three-neck round bottom flask equipped with a condenser and a stirrer 62.87 g (0.392 mol), poly(propylene glycol) 210.21 g, and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 1.10 g were dissolved in 294 g of cyclohexanone. 4,4-diphenylmethane diisocyanate (MDI) 131.39 g (0.525 mol), hexamethylene diisocyanate (HDI) 88.30 g (0.525 mol), cyclohexanone 239 g and as a catalyst were added thereto. 1.76 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was heated and stirred at 60 ° C for 5 hours. Then, using methanol 13 mL was diluted and stirred for 30 minutes to obtain 1100 g of an acid-modified vinyl group-containing polyurethane binder P-2 solution (solid content: 50% by mass). The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a weight average molecular weight of 20,000, a solid content acid value of 46 mgKOH/g, and an ethylenically unsaturated group content of 0.71 mmol/g.

Preparation Example 4 Synthesis of Acid-Modified Ethylenic Unsaturated Resin P-3 having a polymerization inhibiting structure

2,2-bis(hydroxymethyl)propionic acid (DMPA) 46.56 g (0.347 mol) and glycerol monomethacrylate (GLM) in a 2 L three-neck round bottom flask equipped with a condenser and a stirrer 99.93 g (0.624 mol), poly(propylene glycol) 179.01 g, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo 1.10 g were dissolved in 284 g of cyclohexanone. 4,4-diphenylmethane diisocyanate (MDI) 74.11 g (0.296 mol), hexamethylene diisocyanate (HDI) 149.42 g (0.888 mol), cyclohexanone 243 g and as a catalyst were added thereto. 1.75 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was heated and stirred at 60 ° C for 7 hours. Then, it was diluted with 15 mL of methanol, and stirred for 30 minutes to obtain 1100 g of an acid-modified vinyl group-containing polyurethane binder P-3 solution (solid content: 50% by mass). The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a weight average molecular weight of 19,000, a solid content acid value of 35 mgKOH/g, and an ethylenically unsaturated group content of 1.1 mmol/g.

Preparation Example 5 Synthesis of Acid-Modified Ethylenic Unsaturated Resin P-4 having a Polymerization Inhibitory Structure

2,2-bis(hydroxymethyl)propionic acid (DMPA) 46.56 g (0.347 mol) and glycerol monomethacrylate (GLM) in a 2 L three-neck round bottom flask equipped with a condenser and a stirrer 99.93 g (0.624 mol), poly(propylene glycol) 179.01 g, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 1.10 g was dissolved in 284 g of cyclohexanone. 4,4-diphenylmethane diisocyanate (MDI) 74.11 g (0.296 mol), hexamethylene diisocyanate (HDI) 149.42 g (0.888 mol), cyclohexanone 243 g and as a catalyst were added thereto. 1.75 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was heated and stirred at 60 ° C for 7 hours. Then, it was diluted with 15 mL of methanol, and stirred for 30 minutes to obtain 1100 g of an acid-modified vinyl group-containing polyurethane binder P-4 solution (solid content: 50% by mass). The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin had a weight average molecular weight of 19,000, a solid content acid value of 35 mgKOH/g, and an ethylenically unsaturated group content of 1.1 mmol/g.

The storage stability was evaluated in the following manner for the following adhesive solution a to the binder solution g.

Adhesive solution a: the adhesive P-1 solution obtained in the above Preparation Example 2

Binder solution b: the binder P-2 solution obtained in the above Preparation Example 3

Binder solution c: the binder P-3 solution obtained in the above Preparation Example 4

Adhesive solution d: the adhesive P-4 solution obtained in the above Preparation Example 5

Adhesive solution e: a solution obtained by adding 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo 0.55 g to the solution of the above Preparation Example 1 and stirring and dissolving

Binder solution f: 4-hydroxy group added to the solution of the above Preparation Example 1 -2,2,6,6-tetramethylpiperidine-1-oxo 1.10 g, stirred and dissolved solution

Binder solution g: a binder solution obtained by the same method as the above Preparation Example 1 (S-1 solution) except that phenylhydrazine was not added during the synthesis.

-Save stability -

The binder solution a to the binder solution g were stored at a temperature of 60 ° C for 2 weeks, and the degree of gelation after storage was evaluated in accordance with the following evaluation criteria. The results are shown in Table 1 below. Further, the storage stability shown in Table 1 indicates the evaluation results of the storage stability of the binder solution a to the binder solution g used, and the photosensitive resin composition using the binder solution a to the binder solution g was also obtained. the result of.

[evaluation benchmark]

A: No change in molecular weight and viscosity was observed within 2 weeks.

B: The molecular weight or viscosity change was confirmed within 3 days to less than 2 weeks.

C: A change in molecular weight or viscosity was confirmed in less than 3 days.

<Examples, Comparative Examples>

The binder solution a to the binder solution g and the respective components were mixed with each of the components shown in the following Table 1 (part: mass parts), and kneaded by a three-roll mill to obtain a photosensitive resin composition (resistance Agent ink) (Inventive product 1 to invention 4, comparative product 1 to comparative product 3).

- Shortest development time -

The above-mentioned inventive product 1 to invention 4 and comparative product 1 to comparative product 3 were all applied onto a copper foil substrate by screen printing, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes, and allowed to cool to After room temperature, a 1% Na ₂ CO ₃ aqueous solution at 30° C. was developed at a time interval of 5 seconds between 10 seconds and 60 seconds at a spray pressure of 0.15 MPa to visually confirm the development residue of the dried coating film. There is no. The time when the coating film completely disappeared was taken as the shortest development time in each of the examples and the comparative examples.

- Exposure sensitivity -

The inventive product 1 to the invention 4 and the comparative product 1 to the comparative product 3 were all applied onto a copper foil substrate by a screen printing method, and dried at 80 ° C for 30 minutes using a hot air circulating drying oven. After allowing to cool to room temperature, exposure was carried out, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.15 MPa at a time of 1.5 times the shortest development time, and a hot air circulation type was used. The drying oven was thermally hardened at 150 ° C for 60 minutes, and then cooled to room temperature, and a pattern of a circular hole shape having a diameter of 100 μm was attempted.

The exposure sensitivity was evaluated based on the following evaluation criteria based on the amount of exposure necessary to form a pattern of a circular hole shape having a diameter of 100 μm. The results are shown in Table 1 above.

[evaluation benchmark]

AA: A pattern can be formed with an exposure amount of less than 300 mJ/cm ² .

A: A pattern cannot be formed with an exposure amount of less than 300 mJ/cm ² , and a pattern can be formed with an exposure amount of 300 mJ/cm ² or more and less than 400 mJ/cm ² .

B: A pattern cannot be formed with an exposure amount of less than 400 mJ/cm ² , and a pattern can be formed with an exposure amount of 400 mJ/cm ² or more and less than 500 mJ/cm ² .

C: A pattern could not be formed with an exposure amount of less than 500 mJ/cm ² .

-Development residue -

Based on the above shortest development time, the development residue was evaluated in accordance with the following evaluation criteria. The results are shown in Table 1 above.

[evaluation benchmark]

A: The shortest development time is less than 10 seconds.

B: The shortest development time is 10 seconds or more and less than 20 seconds.

C: The shortest development time is 20 seconds or more.

As shown in the above Table 1, in the binder solution of the acid-modified ethylenically unsaturated group-containing resin having no polymerization inhibiting structure at any end of the main chain, it is impossible to mix a sufficient amount of the polymerization inhibitor. Obtain sufficient storage stability (refer to the column of Comparative Product 1 to Comparative Product 3). Further, in the case where sufficient storage stability is ensured by blending a polymerization inhibitor, the exposure sensitivity is rather lowered (refer to the column of Comparative Product 2).

On the other hand, the acid-modified ethylenically unsaturated group-containing resin solution having a polymerization inhibiting structure at at least one end of the main chain has high storage stability even in the absence of a polymerization inhibitor. In addition, the photosensitive resin composition of Invention No. 1 to Invention 4 of the present invention, which is an acid-modified ethylenically unsaturated group-containing resin having a polymerization inhibiting structure at least one end of the main chain, is similarly used. It was confirmed that the storage stability was also high in the absence of a polymerization inhibitor. On the other hand, in general, the storage stability of the present invention, the photosensitive resin composition of the invention 1 to the invention 4 unexpectedly shows good exposure sensitivity. Further, it is also known that the development residue is also suppressed, and it has excellent performance as a photosensitive resin composition for forming a pattern (refer to the column of the invention 1 to the invention 4).

The present invention has been described in connection with its embodiments, but it is to be understood that the invention may not be limited to any of the details of the invention, unless otherwise specified, without departing from the spirit and scope of the invention as set forth in the appended claims. Extensive A general explanation.

The present application claims priority to Japanese Patent Application No. 2012-005067, filed on Jan. .

Claims (18)

A photosensitive resin composition comprising: (A) a binder resin comprising an acid-modified ethylenically unsaturated group-containing resin, wherein the acid-modified ethylenically unsaturated group-containing resin is contained at at least one end of the main chain a structure having a radical polymerization inhibiting ability; (B) a radical polymerizable compound; (C) a thermal crosslinking agent; and (D) a photopolymerization initiator. The photosensitive resin composition according to claim 1, wherein the structure having the radical polymerization inhibiting ability is represented by the following general formula (PIa) or general formula (PIb): In the formula (PIa) and the formula (PIb), R ^T1 represents a hydrogen atom or an aliphatic group; and R ^T2 represents a hydrogen atom, an aliphatic group or an oxygen radical. The photosensitive resin composition according to claim 1 or 2, wherein the binder resin of the above (A) is an acid-modified polyurethane resin containing an ethylenically unsaturated group. The photosensitive resin composition according to claim 3, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a partial structure represented by the following formula (U1): In the formula (U1), L ^U1 represents an ethylenically unsaturated group and a divalent linking group which does not contain a carboxyl group. The photosensitive resin composition according to claim 4, wherein L ^U1 in the above formula (U1) is -(CH ₂ CH ₂ O)n ^U1 CH ₂ CH ₂ -, -[CH ₂ CH( CH ₃ )O]n ^U1 -CH ₂ CH(CH ₃ )-, -(CH ₂ CH ₂ CH ₂ CH ₂ O)n ^U1 -CH ₂ CH ₂ CH ₂ CH ₂ -, the following formula (LL1) The structure shown, the structure represented by the following general formula (LL2), the structure represented by the following general formula (LL3), or the structure represented by the following formula (LL4): Here, n ^U1 to n ^U4 , n and n′ each independently represent a number of 1 or more; and R ^LL1 , R ^LL2 and R each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group. The photosensitive resin composition according to claim 4, wherein the molecular weight of L ^U1 in the above formula (U1) is from 400 to 8,000. The photosensitive resin composition according to claim 6, wherein the molecular weight of L ^U1 in the above formula (U1) is from 500 to 5,000. The photosensitive resin composition according to claim 3, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a partial structure represented by the following formula (UE1): In the general formula (UE1), the L ^UE is a divalent linking group which does not contain -NHC(=O)O- or -OC(=O)NH- in the bond of the main chain, and has one on the side chain. a divalent linking group of an ethylenically unsaturated group. The photosensitive resin composition according to claim 8, wherein the main chain of the L ^UE in the above formula (UE1) bonded to the oxygen atom of the two urethane bonds comprises a divalent aliphatic group, An oxygen atom, a nitrogen atom, a sulfur atom or a combination thereof. The photosensitive resin composition according to claim 8, wherein the above formula (UE1) is represented by the following formula (G1): In the formula (G1), R ¹ to R ³ each independently represent a hydrogen atom or a substituent, A represents a divalent organic group, and X represents an oxygen atom, a sulfur atom or -N(R ¹² )-; wherein R ¹² represents A hydrogen atom or a substituent. The photosensitive resin composition according to claim 3, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a weight average molecular weight of 5,000 to 60,000, and the acid value of the solid component is 10 mgKOH/g~120 mgKOH/g, and the content of ethylenic unsaturated groups is 0.05 mmol/g~1.2 mmol/g. The photosensitive resin composition according to claim 4, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin is represented by HO-L ^U1 -OH (L ^U1 ) The solid content ratio of the ethylenically unsaturated group and the carboxyl group-free divalent linking group is 10% to 60% of the partial structure represented by the above formula (U1). The photosensitive resin composition according to claim 3, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin is at least one diisocyanate compound having an ethylenically unsaturated group. And at least one diol compound having two hydroxyl groups, and at least one diol compound having a carboxyl group and two hydroxyl groups are each reacted with at least one diol compound having no ethylenic unsaturated group or carboxyl group. Resin. The photosensitive resin composition according to claim 13, wherein the diisocyanate compound has a 2,2-diphenylpropane type, a diphenylmethane type, a biphenyl type, a naphthalene type, a phenanthrene type or an anthracene type. Skeleton. A photosensitive laminate comprising a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 14 on the substrate. A flexible circuit substrate having a substrate as claimed The photosensitive layer of the photosensitive resin composition according to any one of the items 1 to 14 of the invention, which has a resist pattern obtained by photocuring the photosensitive layer. The flexible circuit board according to claim 16, wherein the substrate is a polyimide film. A method of forming a permanent pattern, comprising the step of exposing a photosensitive layer formed using the photosensitive resin composition according to any one of claims 1 to 14.