JP2013041237A - Photosensitive composition, photosensitive dry film, photosensitive laminate, flexible wiring board, manufacturing method of flexible wiring board, and permanent pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which is excellent in insulation, folding resistance, resolution and flame retardancy, a photosensitive dry film, photosensitive laminate, a flexible wiring board, a manufacturing method of a flexible wiring board, and a permanent pattern forming method.SOLUTION: A photosensitive composition contains a binder resin, a polymerizable compound, a photoinitiator and a heat crosslinking agent, where an acid-modified ethylenically unsaturated group-containing polyurethane resin and an acid-modified ethylenically unsaturated group-containing epoxy resin having a certain partial structure on the side chain are contained as the binder resin, and the acid-modified ethylenically unsaturated group-containing polyurethane resin has a certain partial structure, a mass average molecular amount of 5,000 to 60,000, a solid content acid value of 20 mgKOH/g to 120 mgKOH/g and an ethylenically unsaturated group equivalent of 0.5 mmol/g to 2.0 mmol/g. Using this, provided are a photosensitive dry film, a photosensitive laminate, a flexible wiring board, a manufacturing method of a flexible wiring board, and a permanent pattern forming method.

Description

  The present invention relates to a photosensitive composition, a photosensitive dry film, a photosensitive laminate, a flexible wiring substrate, a method for producing a flexible wiring substrate, and a method for forming a permanent pattern, which are suitable as a solder resist material for flexible substrates.

  Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film in which a photosensitive layer is formed by coating a photosensitive composition on a support and drying it has been used. As a method for forming a permanent pattern such as a solder resist, for example, a photosensitive film is laminated on a substrate such as a copper-clad laminate on which a permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate is formed. There is known a method of forming a permanent pattern by performing exposure on the substrate, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.

  In the photosensitive composition that can be used for the solder resist, particularly when used for a flexible wiring board, it is one of important issues to improve insulation, folding resistance, resolution, and flame retardancy, Various studies have been made.

  Known photosensitive binder resins include acid-modified vinyl group-containing epoxy resins, acid-modified ethylenically unsaturated group-containing polyurethane resins, acid-modified unsaturated group-containing polyester resins, and acid-modified ethylenically unsaturated group-containing acrylic resins. These combinations have also been proposed. For example, a combination of an acid-modified vinyl group-containing epoxy resin and an acrylic resin (see Patent Document 1), an acid-modified unsaturated group-containing polyester resin, a polyhydric alcohol, a diisocyanate, and a urethane acrylate resin synthesized from a hydroxyl group-containing acrylate A combination (see Patent Document 2), a combination of a specific acid-modified vinyl group-containing epoxy resin and a specific acid-modified ethylenically unsaturated group-containing polyurethane resin (see Patent Documents 3 and 4) is disclosed or proposed.

  However, demands for solder resists, especially flexible wiring boards, are becoming increasingly sophisticated, and these proposed technologies are not always satisfactory for improving insulation, folding resistance, resolution and flame retardancy. It is not possible.

  Therefore, a photosensitive composition, a photosensitive dry film, a photosensitive laminate, a flexible wiring board, a method for manufacturing a flexible wiring board, and a permanent pattern formation that are all excellent in insulation, folding resistance, resolution, and flame retardancy Currently, there is a demand for provision of methods.

JP 2007-256943 A JP 2007-128059 A JP 2006-11395 A JP 2009-251585 A

  The present invention addresses the above-described problems and achieves the following objects. That is, the present invention is a photosensitive composition excellent in insulation, folding resistance, resolution and flame retardancy, photosensitive dry film, photosensitive laminate, flexible wiring board, method for producing a flexible wiring board, It is another object of the present invention to provide a permanent pattern forming method.

Means for solving the problems are as follows. That is,
(1) It contains a binder resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. As the binder resin, at least one acid-modified ethylenically unsaturated group-containing polyurethane resin and a side chain represented by the following general formula ( EP) containing at least one acid-modified ethylenically unsaturated group-containing epoxy resin having a partial structure represented by the following general formula (UE1): It has a partial structure represented, has a mass average molecular weight of 5,000 to 60,000, an acid value of solid content of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.00. The photosensitive composition characterized by being 5 mmol / g-2.0 mmol / g.

In the general formula (EP), one of R ^A1 and R ^A2 represents an unsaturated aliphatic group, and the other represents a saturated or unsaturated aliphatic group having a carboxyl group or an aromatic group having a carboxyl group. Represent. R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom or a substituent.

In the general formula (UE1), L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, and is an ethylenically unsaturated group. Represents a divalent linking group in which one group having a substituent is substituted.
(2) The photosensitive composition as described in (1) in which the group having an ethylenically unsaturated group substituted for the L ^UE has a group represented by any one of the following general formulas (1) to (3).

In General formula (1), R < ¹ > -R < ³ > represents a hydrogen atom or monovalent organic group each independently. X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In General formula (2), R < ⁴ > -R < ⁸ > represents a hydrogen atom or monovalent organic group each independently. Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents a hydrogen atom or a monovalent organic group.
(3) The photosensitive composition as described in (1) or (2) in which the acid-modified ethylenically unsaturated group-containing polyurethane resin has a partial structure represented by the following general formula (U1).

In the general formula (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.
(4) The photosensitive composition according to (3), wherein L ^U1 in the general formula (U1) has a molecular weight in terms of HO—L ^U1 —OH of 400 to 8,000.
(5) The photosensitive composition according to (3), wherein L ^U1 in the general formula (U1) has a molecular weight in terms of HO—L ^U1 —OH of 500 to 5,000.
(6) The photosensitive composition according to any one of (1) to (5), wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a group having a carboxyl group at a polymer terminal.
(7) The photosensitivity according to any one of (1) to (6), wherein the acid-modified ethylenically unsaturated group-containing epoxy resin is represented by any one of the following general formulas (P1) to (P3). Sex composition.

In the general formulas (P1) to (P3), R ^e1 represents a group represented by the general formula (EP) or an epoxy group. R ^e3 represents a hydrogen atom or a methyl group. R ^e3 and ^e3 each independently represent a hydrogen atom, an alkyl group or an aryl group. n ^{e1 to} n ^e3 each independently represents a number of 1 or more. However, R ^e1 is not ^{entirely an} epoxy group in the molecule. Further, a plurality of R ^e1 present in the molecule may be the same or different from each other, a plurality of R ^e3 to R ^e5 present in the molecule may be the same or different from each other. Y represents —O—, —C (═O) —O—, —O—C (═O) — or —N (Rx) —. Here, Rx represents a hydrogen atom or a substituent. La is an alkylene group or ^a divalent group having —O—, —C (═O) —O—, —O—C (═O) — or —O—C (═O) —O— in the linking chain. Represents a linking group. L ^b represents a divalent linking group having at least an alkyl partial structure, a cycloalkyl partial structure, or an aryl partial structure. L ^c and L ^d each independently represent a divalent linking group.
(8) The photosensitivity according to (7), wherein the acid-modified ethylenically unsaturated group-containing epoxy resin is represented by any one of the following general formulas (P1-1) to (P3-1): Sex composition.

In the general formulas (P1-1) to (P3-1), R ^e1 represents a group represented by the general formula (EP) or an epoxy group. R ^e2 and R ^e3 each independently represent a hydrogen atom or a methyl group, and R ^{e4 to} R ^e9 each independently represent a hydrogen atom, an alkyl group, or an aryl group. n ^e1 and n ^e2 each independently represent a number of 1 or more, and n ^e3 represents 0 or a number of 1 or more. However, R ^e1 is not ^{entirely an} epoxy group in the molecule. A plurality of R ^e1 present in the molecule may be the same or different, and a plurality of R ^e2 and R ^e3 present in the molecule may be the same or different. In R ^{e4 to} R ^e9 , each of the plurality of R ^{e4 to} R ^e9 present in the molecule may be the same as or different from each other.
(9) The photosensitive composition according to (8), wherein the acid-modified ethylenically unsaturated group-containing epoxy resin is represented by the general formula (P3-1).
(10) Any one of (1) to (9), wherein either R ^A1 or R ^A2 in the general formula (EP) is —CH═CH ₂ or —C (CH ₃ ) ═CH ₂ The photosensitive composition as described in any one of.
(11) The ratio of the acid-modified ethylenically unsaturated group-containing urethane resin in the total solid mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the acid-modified ethylenically unsaturated group-containing epoxy resin is: The photosensitive composition of any one of (1)-(10) which is 55 mass% or more and 95 mass% or less.
(12) The photosensitive composition according to any one of (1) to (11), further comprising a phosphorus-based flame retardant.
(13) A photosensitive dry film comprising the photosensitive composition according to any one of (1) to (12) on a carrier film.
(14) A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of (1) to (12) on a substrate.
(15) having a photosensitive layer containing the photosensitive composition according to any one of (1) to (12) on a substrate, and having a resist pattern obtained by photocuring the photosensitive layer A flexible wiring board characterized by comprising:
(16) The flexible wiring board according to (15), wherein the substrate is a polyimide film.
(17) A photosensitive dry film obtained by applying and drying the photosensitive composition according to any one of (1) to (12) on a carrier film, and then using the photosensitive dry film. A method for producing a flexible wiring board, comprising: forming a photosensitive layer on a substrate; and exposing and developing the photosensitive layer to form a resist pattern.
(18) A method for forming a permanent pattern, wherein the photosensitive layer containing the photosensitive composition according to any one of (1) to (12) is exposed.

  According to the present invention, a photosensitive composition having excellent insulation, folding resistance, resolution and flame retardancy, photosensitive dry film, photosensitive laminate, flexible wiring board, flexible wiring board manufacturing method, and permanent pattern formation A method can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains an acid-modified ethylenically unsaturated group-containing polyurethane resin and an acid-modified ethylenically unsaturated group-containing epoxy resin as a binder resin, a polymerizable compound, and a photopolymerization initiator. And, if necessary, other components such as a thermal crosslinking agent, an inorganic filler, and a flame retardant.

<< Acid-modified ethylenically unsaturated group-containing polyurethane resin >>
The acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected according to the purpose. In the present invention, in particular, the acid-modified polyurethane having an ethylenically unsaturated bond in the side chain Resins are preferred. In the present invention, the side chain is a chain that is connected by substituting from a chain of atoms constituting the main chain of the polyurethane resin with a branched or substituted atom constituting the main chain, and has an ethylenically unsaturated group in the side chain. Means that an ethylenically unsaturated group is contained in such a side chain, or an atom constituting the main chain is directly substituted with an ethylenically unsaturated group. For example, a polyurethane resin obtained only by reaction of a diol of HOCH ₂ CH═CHCH ₂ OH and OCN (CH ₂ ) ₆ NCO contains an ethylenically unsaturated group in the main chain. In addition, the part by which the polymer terminal was sealed by the ethylenically unsaturated group containing compound is not a side chain.
The ethylenically unsaturated group is a group having an ethylene bond that is consumed in the measurement of bromine value and iodine value, and is not a group showing aromaticity such as benzene. The ethylenically unsaturated group is preferably a vinyl group which may have a substituent.

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

<< Molecular weight >>
There is no restriction | limiting in particular as a mass mean molecular weight of acid-modified ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 5,000-60,000 are preferable, 5,000-50 Is more preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 5,000, when the photosensitive composition of the present invention is used for a photosensitive solder resist, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained. If it exceeds 60,000, coating suitability and developability may be deteriorated. In addition, when an inorganic filler is used, it is excellent in the dispersibility of the inorganic filler, excellent in crack resistance and heat resistance, and excellent in developability of non-image areas with an alkaline developer.
Here, the mass average molecular weight is determined using, for example, a high-speed GPC apparatus (manufactured by Toyo Soda Co., Ltd., HLC-802A), a 0.5 mass% THF solution as a sample solution, and the column is TSKgel HZM-M 1. Using a book, 200 μL of sample can be injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm). And the mass mean molecular weight was calculated | required from the molecular weight distribution curve calibrated with the standard polystyrene.

<< 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 intended purpose, but is preferably 20 mgKOH / g to 120 mgKOH / g, and 30 mgKOH / g to 110 mgKOH / g is more preferable, and 35 mgKOH / g to 100 mgKOH / g is particularly preferable. If the acid value is less than 20 mg KOH / g, the developability may be insufficient, and if it exceeds 120 mg KOH / g, the development speed may be too high, and development control may be difficult.
Here, the acid value can be measured in accordance with, for example, JIS K0070. In addition, when a sample does not melt | dissolve, a dioxane or tetrahydrofuran is used as a solvent. The acid value is the solid content acid value of the resin.

<< Equivalent ethylenically unsaturated group >>
The ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing polyurethane resin used in the present invention is preferably 0.5 mmol / g to 2.0 mmol / g, and 0.5 mmol / g to 1.9 mmol / g. Is more preferable, and 0.75 mmol / g to 1.8 mmol / g is particularly preferable. By adjusting the ethylenically unsaturated group equivalent to such a range, the effects of the present invention can be effectively achieved.
Here, the ethylenically unsaturated group equivalent can be determined, for example, by measuring the bromine number. The bromine number can be measured, for example, according to JIS K2605.
Here, the ethylenically unsaturated equivalent is typically a vinyl group equivalent, and the number of grams of bromine (Br ₂ ) added to 100 g of the resin to be measured obtained by the bromine number (gBr ₂ / 100 g) is converted to the number of moles of added bromine (Br ₂ ) per 1 g of resin.

Below, the acid-modified urethane resin which has an ethylenically unsaturated bond in the side chain preferable in this invention is demonstrated.
The acid-modified urethane resin having an ethylenically unsaturated bond in the side chain used in the present invention has a partial structure represented by the following general formula (UE1).

In the general formula (UE1), L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, and is an ethylenically unsaturated group. Represents a divalent linking group in which one group having a substituent is substituted.
Here, there is no restriction | limiting in particular as an ethylenically unsaturated group, According to the objective, it can select suitably, For example, at least 1 among the functional groups represented by following General formula (1)-(3) The thing which has is mentioned.

In General formula (1), R < ¹ > -R < ³ > represents a hydrogen atom or monovalent organic group each independently. Here, examples of the monovalent organic group include 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, and an arylthio group. , Amino group, alkylamino group, arylamino group, acylamino group, sulfonamido group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbamoyl group, sulfamoyl Group, hydroxyl group, mercapto group, cyano group, nitro group, carboxyl group, sulfo group, ureido group, urethane group and the like, and these groups may be further substituted with these substituents. In addition, the same group is mentioned also in each subsequent group and the monovalent organic group or substituent in each general formula.
R ¹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituted group. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. Among them, a hydrogen atom, a carboxyl group, an alkoxy group are preferable because of high radical reactivity. A carbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

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 among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable in terms of high radical reactivity.
Here, the substituent that each of the above groups may have (substituent that may be present in an alkyl group that may have a substituent) is not particularly limited, and may be appropriately selected depending on the purpose. For example, the groups mentioned in the above-mentioned monovalent organic groups can be mentioned, and halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups Amino group, alkylamino group, arylamino group, acylamino group, carbamoyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carboxyl group, sulfo group, nitro group, and cyano group are preferred.

In General formula (2), R < ⁴ > -R < ⁸ > represents a hydrogen atom or monovalent organic group each independently. R ^{4 to} R ⁸ are not particularly limited and may be appropriately selected depending on the purpose. Here, examples of the monovalent organic group include those described as R ^{1 to} R ³ in the general formula (1). Groups. R ^{4 to} R ⁸ are a hydrogen atom, a halogen atom, an amino group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, or an arylamino which may have a substituent. Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent , An aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. An atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

Examples of the substituent that each of the above groups may have include the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R ¹² has the same meaning as R ^{12 in} the general formula (1), and preferred examples thereof are also the same.

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. Here, as a monovalent organic group, the group quoted by R < ¹ > -R < ³ > in the said General formula (1) is mentioned. R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity. R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, an amino group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, or an arylamino which may have a substituent. Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent , An aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. An atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

Here, as a substituent which each said group may have, the thing similar to General formula (1) is mentioned. Further, Z is an oxygen atom, a sulfur atom, -N ^{(R 13)} -, or a phenylene 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 high radical reactivity.

Of the groups represented by the general formulas (1) to (3), the group represented by the general formula (1) is preferable, and R ¹ in the general formula (1) is a methyl group from the viewpoint of forming a crosslinked cured film. And a group in which R ² and R ³ are hydrogen atoms, a group in which R ^{1 to} R ³ in the general formula (1) are all hydrogen atoms, and a styryl group in which Z in the general formula (3) is a phenylene group are preferable. A group in which R ¹ in the general formula (1) is a methyl group and R ² and R ³ are hydrogen atoms, and a group in which R ^{1 to} R ³ in the general formula (1) are all hydrogen atoms are more preferable. From the viewpoint of achieving both the formability of the cured film and the raw storage stability, a group in which R ¹ in the general formula (1) is a methyl group and R ² and R ³ are hydrogen atoms is particularly preferable. Here, X in the general formula (1) is preferably an oxygen atom, and the ethylenically unsaturated group is preferably a methacryloyloxy group or an acryloyloxy group, and most preferably a methacryloyloxy group.

In order to introduce an ethylenically unsaturated group into the side chain, (i) a method obtained by a polymerization reaction with a compound having an ethylenically unsaturated group in a diisocyanate compound or a diol compound, (ii) a carboxyl group-containing polyurethane, and a molecule There is a method obtained by reacting an epoxy group with a compound having an ethylenically unsaturated group.
In the present invention, any method may be used as long as it has a partial structure represented by the general formula (UE1).
Hereinafter, the polyurethane resin obtained by the method (i) is also referred to as polyurethane resin (i), and the polyurethane resin obtained by the method (ii) is also referred to as polyurethane resin (ii). The polyurethane resin having an ethylenically unsaturated bond in the side chain includes both polyurethane resins (i) and (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 a reaction of a diisocyanate compound and a diol compound (a compound having at least two hydroxyl groups), and the polyurethane resin (i) is composed of at least one diisocyanate compound represented by the following general formula (4): It is a polyurethane resin having as a basic skeleton a structural unit represented by a reaction product of at least one diol compound represented by the following general formula (5).

^OCN-X 0 -NCO ··· general Formula (4)
HO-Y ⁰ -OH General formula (5)

In the general formulas (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 general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If it has at least one of them, as a reaction product of the diisocyanate compound and the diol compound, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is provided. Generated. According to this method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is easier than substitution and introduction of a desired side chain after the reaction of the polyurethane resin is generated. Can be manufactured.

The diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose. For example, a triisocyanate compound and a monofunctional alcohol having an unsaturated group Or the product obtained by addition-reacting with 1 equivalent of monofunctional amine compounds is mentioned.
The triisocyanate compound is not particularly limited and can be appropriately selected depending on the purpose. For example, the compounds described in paragraphs [0034] to [0035] of JP-A-2005-250438, Etc.

  The monofunctional alcohol having an unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs of JP-A-2005-250438 And the compounds described in [0037] to [0040].

  There is no restriction | limiting in particular as a diisocyanate compound in the method using the diisocyanate compound containing an unsaturated group in a side chain, It can select suitably according to the objective, Monofunctional alcohol which has a triisocyanate compound and an unsaturated group, or A diisocyanate compound obtained by addition reaction with 1 equivalent of a monofunctional amine compound, for example, unsaturated in the side chain described in paragraphs [0042] to [0049] of JP-A-2005-250438 And a compound having a group.

  The polyurethane resin (i) is a diisocyanate compound other than the diisocyanate compound containing an ethylenically unsaturated group, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. It can also be copolymerized.

  The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a diisocyanate compound represented by the following general formula (6).

^OCN-L 1 -NCO ··· general formula (6)

In General Formula (6), L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, for example, an ester group, a urethane group, an amide group, or a ureido group.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (6), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4 ' -Aromatic diisocyanate compounds such as diisocyanates; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; Isophorone diisocyanate, 4,4'-methyl Alicyclic diisocyanate compounds such as bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 A diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate;

The diisocyanate compound represented by the general formula (4) or (6) (particularly the diisocyanate compound represented by the general formula (6)) may be used in combination of different types, but the folding resistance can be improved. At least one of them is preferably an aromatic diisocyanate compound. The aromatic diisocyanate compound is preferably a diisocyanate compound having a bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, or anthracene type skeleton, for example, a bisphenol A type or bisphenol F type skeleton. More preferred is a diisocyanate compound having
Each of these types of skeletons is 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 each independently represents an integer of 0 to 4. l ₁ and l ₂ are preferably 0 or 1. l ₃ represents an integer of 0-6. l ₄ represents an integer of 0 to 8. l ₃ is preferably 0 to 2, and l ₄ is preferably 0 or 2. When l _{1 to} l ₄ is 2 or more, a plurality of R ^a and R ^b may be the same as or different from each other.

  The diisocyanate compound is more preferably a combination of an aromatic diisocyanate compound and an aliphatic diisocyanate compound from the viewpoint of suppressing warping after curing and improving folding resistance. The aromatic diisocyanate compound is preferably a diisocyanate compound having a bisphenol A-type, bisphenol F-type, biphenyl-type, naphthalene-type, phenanthrene-type, or anthracene-type skeleton, such as a bisphenol A-type or bisphenol F-type skeleton. The diisocyanate compound is more preferable. As the aliphatic diisocyanate compound, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate are preferable, and hexamethylene diisocyanate and trimethylhexamethylene diisocyanate are more preferable.

  There is no restriction | limiting in particular as a diol compound represented by the said General formula (5), According to the objective, it can select suitably, For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound etc. are mentioned. .

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

  As such a diol compound having an ethylenically unsaturated group, a compound represented by the following general formula (UE) is preferable, and in the polyurethane resin used in the present invention, the general formula (UE1) It will have the partial structure represented.

In general formula (UE), L ^UE is synonymous with L ^UE represented by the said general formula (UE1), and its preferable range is also the same. That is, L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, and 1 ethylenically unsaturated group in the side chain. Represents a divalent linking group.

  The compound represented by the general formula (UE) is preferably a compound represented by the following general formulas (UE-1) to (UE-6).

In General Formulas (UE-1) to (UE-6), E ¹ represents a single bond or a divalent linking group (a divalent organic residue), and E ² represents a single bond or ₂ other than —CH ₂ —. Represents a valent linking group. A represents a divalent linking group. Q represents any group of the general formulas (1) to (3). Examples of the divalent linking group for 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. Here, Q represents any group of the general formulas (1) to (3).
Specific examples of these compounds include compounds described in paragraphs “0057” to “0060” of JP-A-2005-250438.

  Of the compounds represented by the general formulas (UE-1) to (UE-6), the compound represented by the general formula (UE-6) is preferable. Of the compounds represented by the general formula (UE-6), compounds represented by the following general formula (G) are particularly preferable. Note that the compound represented by the general formula (G) has a partial structure represented by the following general formula (G1) in the polyurethane resin.

In General Formulas (G) and (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, sulfur Represents an atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, the general formula (G), ^R 1 to R ³ and X in (G1) has the same meaning as ^R 1 to R ³ and X in the general formula (1), preferred embodiments versa.
Examples of the compound represented by the general formula (G) include compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438, and are preferable in the present invention.
By using the polyurethane resin derived from the diol compound represented by the general formula (G), the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.

  The polyurethane resin (i) of the present invention is acid-modified, and examples of the acid in the acid modification include carboxylic acid and sulfonic acid, and carboxylic acid is particularly preferable. For the synthesis of the polyurethane resin (i), it is preferable to use acid-modified by using a diol compound having a carboxyl group. Examples of the diol compound having a carboxyl group include those represented by the following formulas (17) to (19).

In the formulas (17) to (19), R ¹⁵ represents a hydrogen atom or a substituent (for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH ₂ , —COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms. ) And the like, as long as it represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group that may have a substituent, and is appropriately selected depending on the purpose. A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable. In the formulas (17) to (19), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may be a single bond or a substituent (for example, an alkyl group, an aralkyl group or an aryl group). As long as it represents a divalent aliphatic or aromatic hydrocarbon group that may have an alkyl group, and an alkoxy group and a halogen atom are not particularly limited, and can be appropriately selected depending on the purpose. However, a C1-C20 alkylene group and a C6-C15 arylene group are preferable, and a C1-C8 alkylene group is more preferable. If necessary, the L ^{9 to} L ¹¹ may have another functional group that does not react with the isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. In addition, you may form a ring by two or three of said R < ¹⁵ >, L < ⁹ >, L < ¹⁰ >, L < ¹¹ >.
In the formula (18), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. However, an aromatic group having 6 to 15 carbon atoms is preferable.

  The diol compound having a carboxyl group represented by the formulas (17) to (19) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxybenzoic acid, 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-hydroxy 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-propionamide and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a diol compound which has a carboxyl group, According to the objective, it can select suitably, For example, the compound described in Paragraph [0047] of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  The presence of such a carboxyl group is preferable because the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. By introducing a carboxyl group in this way, the acid value can be adjusted to the preferred range in the present invention as described above.

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-2005-250438, paragraph [0095] to And the compounds described in [0101].

The polyurethane resin (i) is, for example, a diol compound containing an ethylenically unsaturated group in the side chain from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. Or a diol compound other than a diol compound containing a carboxyl group can be copolymerized. In the present invention, it is particularly preferable to copolymerize such a diol compound.
Such a diol compound is not particularly limited and can be appropriately selected according to the purpose. For example, a low-molecular diol compound or a polymer diol compound such as a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, A polycarbonate compound of m-dihydroxybenzene can be exemplified.

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

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

L ^U1 includes, for example, an alkylene group, an arylene group, and a divalent heterocyclic group, and the alkylene group includes —O—, —OCOO—, a phenylene group, and a carbon-carbon double bond in the chain of the alkylene group. , A carbon-carbon triple bond, -OCO-Z ¹ -COO- (Z ¹ represents an alkylene group, an alkenylene group, or an arylene group).

Of the diol compounds represented by the general formula (U), the low molecular weight diol compound preferably has a mass average molecular weight of less than 400, and is described in, for example, paragraph [0048] of JP-A-2007-2030. And the like.
In the present invention, a polymer diol compound is preferable and will be described in detail below.

-Polymer diol compound-
The polymer diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block copolymer or random copolymer Polyether diols such as coalesced polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol; polyhydric alcohol or polyether diol and maleic anhydride, maleic acid, fumaric acid, Polyester diols that are condensates of polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, terephthalic acid, isophthalic acid; reaction of glycol or bisphenol with carbonate Alternatively, polycarbonate diols obtained by reacting phosgene with glycol or bisphenol in the presence of alkali; caprolactone-modified polymer diols such as caprolactone-modified polytetramethylene diol, polybutadiene-based polymers such as polyolefin-based polymer diols and hydrogenated polybutadiene diols Examples thereof include polymer diols and silicone polymer diols. These may be used individually by 1 type and may use 2 or more types together.

In the present invention, preferred compounds and partial structures are such that L ^U1 in the general formulas (U) and (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 O) n U1 -CH 2 CH 2 CH 2 -, - ^{_{[(CH 2) n U2 -OC (}} = O) ^{_{- (CH 2) n U3 -C}} (= O) O ] _{^{n U4 -O (CH 2) n}} U2 - or - ^{_{[(CH 2) n U5 -OC (}} = O) O ] ⁿ U6 - _(CH 2) n ^U7 −. Here, n ^{U1 to} n ^U7 each independently represents a number of 1 or more.
In addition, the compound represented by the general formula (U) is also preferably a diol compound represented by the following general formulas (III-1) to (III-6).

  The polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438. Can be mentioned.

  The polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs [0077] to [0079] and paragraphs [0083] to [0085] of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like, and the like.

  There is no restriction | limiting in particular as said polycarbonate diol compound, According to the objective, it can select suitably, For example, Unexamined-Japanese-Patent No. 2005-250438 Paragraph [0080]-[0081] and Paragraph [0084] No. 9-No. 12 and the like, and the like.

In addition to the diol compound described above, a diol compound having a substituent that does not react with an isocyanate group can be used in combination.
There is no restriction | limiting in particular as a diol compound which has a substituent which does not react with the said isocyanate group, According to the objective, it can select suitably, For example, Paragraph [0087]-[0088] of Unexamined-Japanese-Patent No. 2005-250438 And the described compounds.

The mass average molecular weight of such a polymer diol compound (molecular weight in terms of HO-L ^U1- OH in L ^U1 in the general formula (U1)) is preferably 400 to 8,000, and preferably 500 to 5,000. Is more preferable, it is more preferable that it is 600-3,000, and it is especially preferable that it is 800-2,000. If the mass average molecular weight is less than 400, sufficient folding resistance may not be obtained, and if it exceeds 8,000, the glass transition temperature (Tg) of the resulting polyurethane resin will be too low. May deteriorate.
Here, the mass average molecular weight is determined using, for example, a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column of one TSKgel HZM-M. In use, 200 μL of sample can be injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).

  The mass ratio of the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is preferably 10 to 60%, more preferably 20 to 60%, and more preferably 25 to 25%. It is more preferable that it is 55%, and it is further more preferable that it is 30 to 50%. When the mass ratio is less than 10%, it may be difficult to suppress warping after curing, and when it exceeds 60%, the sensitivity of photocuring may be excessively lowered and resolution may be deteriorated.

  Moreover, as a polyurethane resin which has an ethylenically unsaturated bond in the side chain used by this invention, what has an unsaturated group in a polymer terminal and a principal chain is used suitably. Polyurethane resin having an ethylenically unsaturated bond in the side chain, or between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased. Here, as an unsaturated group, it is especially preferable to have a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.

As a method for introducing an unsaturated group into the polymer terminal, there are the following methods. That is, in the step of synthesizing the polyurethane resin having an ethylenically unsaturated bond in the side chain as described above, in the step of treating with the residual isocyanate group at the polymer end and the alcohol or amine, the alcohol having an unsaturated group. Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.
The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and can be appropriately selected according to the purpose. The ethylenically unsaturated group equivalent is 0.5 mmol / g to 2.0 mmol / g, 0.5 mmol / g to 1.9 mmol / g is more preferable, and 0.75 mmol / g to 1.8 mmol / g is particularly preferable.

  As a method of introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. The diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the purpose. For example, cis-2-butene-1,4-diol, trans-2-butene- 1,4-diol, polybutadiene diol, and the like.

In the present invention, as the acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention, those having at least one carboxyl group at the terminal of the polymer main chain may be used as non-images by an alkaline developer. It is preferably used because it is excellent in developability of part. It has at least one carboxyl group at the terminal of the polymer main chain and preferably has 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is excellent in developability and has a fine pattern forming property. Is particularly preferable.
The polyurethane resin has two main chain ends, but preferably has at least one carboxyl group at one end, and may have at least one carboxyl group at both ends.

  It is preferable that the terminal of the main chain of the polyurethane resin has a structure represented by the following general formula (AD).

General formula (AD)
-L ^100- (COOH) _n

In the general formula (AD), L ¹⁰⁰ represents an (n + 1) -valent organic linking chain, n represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 2.
The organic linking group represented by L ¹⁰⁰ is configured to include one or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, specifically, represented by L ^100. The number of atoms constituting the main skeleton of the organic linking group is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 10.
The “main skeleton of the organic linking group” means an atom or an atomic group used only for linking the main chain of the polyurethane resin and the terminal COOH, and when there are a plurality of linking paths, The atom or atomic group which comprises the path | route with the fewest number of atoms used is pointed out.

  The method for introducing at least one carboxyl group at the end of the main chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a raw material for producing a polyurethane resin, at least one Examples include a method using a carboxylic acid compound having a carboxyl group.

  Examples of the carboxylic acid compound include a monocarboxylic acid compound having one carboxyl group, a dicarboxylic acid compound having two carboxyl groups, a tricarboxylic acid compound having three carboxyl groups, a tetracarboxylic acid compound having four carboxyl groups, and a carboxyl group. Examples thereof include pentacarboxylic acid compounds having five groups. Among these, a dicarboxylic acid compound having two carboxyl groups is particularly preferable in terms of excellent developability and fine pattern formability.

  The carboxylic acid compound is not particularly limited as long as it has at least one carboxyl group, and can be appropriately selected according to the purpose. However, a compound represented by the following general formula (ADH) is preferable.

General formula (ADH)
^{H-O-L 200 -Y 100} -L 100 - (COOH) n

In the general formula (ADH), L ¹⁰⁰ and n represent the same meaning as in the general formula (AD). Y ¹⁰⁰ represents a divalent or higher valent atom. L ²⁰⁰ represents a single bond or an alkylene group which may have a substituent.
Examples of the divalent or higher atom in Y ¹⁰⁰ include an oxygen atom, a nitrogen atom, a carbon atom, and a silicon atom. Among these, a nitrogen atom and a carbon atom are particularly preferable. Here, the atom represented by Y ¹⁰⁰ being divalent or more means that at least Y ¹⁰⁰ has two bonds in which the terminal —COOH is bonded via L ¹⁰⁰ and L ²⁰⁰ , Y ¹⁰⁰ may further have a hydrogen atom or a substituent.
Examples of the substituent which can be introduced into Y ^100, a hydrogen atom, an oxygen atom, a sulfur atom, a substituted group configured to include an atom selected from a nitrogen atom and a halogen atom. Among these, a hydrocarbon group having 1 to 50 carbon atoms is preferable, a hydrocarbon group having 1 to 40 carbon atoms is more preferable, and a hydrocarbon group having 1 to 30 carbon atoms is particularly preferable.

The alkylene group for L ^200, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms. Examples of the substituent that can be introduced into the alkylene group include a halogen atom (—F, —Br, —Cl, —I), an alkyl group that may have a substituent, and the like.

  The carboxylic acid compound represented by the general formula (ADH) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include lactic acid, malic acid, hydroxyhexanoic acid, citric acid, and a diol compound. Examples include a reaction product of an acid anhydride. These may be used individually by 1 type and may use 2 or more types together. Among these, malic acid is particularly preferable.

  Specific examples of the polyurethane resin (i) used in the present invention include, for example, polymers P-1 to P-31 shown in paragraphs [0293] to [0310] of JP-A-2005-250438. Can be mentioned. Among these, the polymers of P-27 and P-28 shown in paragraphs [0308] and [0309] are preferable.

The polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is prepared by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent and adding a known catalyst having an activity corresponding to each reactivity. To be synthesized. The molar ratio of diisocyanate and diol compound used for synthesis (M _a : M _b ) is not particularly limited and may be appropriately selected depending on the intended purpose, preferably 1: 1 to 1.2: 1. By treating with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.

  The polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is, in particular, the aforementioned diisocyanate compound and a diol compound, a (meth) acrylate compound having two hydroxyl groups in the molecule, and two in the molecule. It is preferably obtained by reacting a carboxylic acid having a hydroxyl group with the above-mentioned polymer diol compound, and in addition, obtained by reacting a compound having one hydroxyl group and a carboxyl group represented by the general formula (ADH). Is preferred.

-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 polyurethane resin obtained by reacting a carboxyl group-containing polyurethane resin containing diisocyanate and a carboxyl group-containing diol as essential components and a compound having an epoxy group and an ethylenically unsaturated group in the molecule. It is.
In the present invention, the partial structure represented by the general formula (UE1) is essential, but the partial structure represented by the general formula (UE1) can also be incorporated by the reaction described above.

Depending on the purpose, the polyurethane resin (ii) may contain a low molecular diol having a mass average molecular weight of 300 or less or a low molecular diol having a mass average molecular weight of 500 or more as a diol component as a copolymer component.
By using this, the polyurethane resin (ii) has excellent dispersibility, crack resistance, and impact resistance with an inorganic filler, so that it has heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties. improves.
In addition, as the polyurethane resin (ii), a diisocyanate of a divalent aliphatic and aromatic hydrocarbon which may have a substituent, a COOH group and two carbon atoms via any one of a C atom and an N atom. A reaction product comprising a carboxyl group-containing diol having an OH group as an essential component, the reaction product obtained, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a -COO- bond It may be obtained by reaction.
Moreover, as said polyurethane resin (ii), the diisocyanate shown by the following general formula (I), and the carboxyl group containing diol compound represented by Formula (17)-(19) demonstrated in the above-mentioned polyurethane resin (i) are mentioned. A high molecular diol having a mass average molecular weight of 800 to 3,000 represented by the following general formulas (III-1) to (III-6) according to the purpose: A reaction product with at least one selected from the group consisting of an epoxy group and an ethylenically unsaturated group in a molecule represented by the following general formulas (IV-1) to (IV-16): It may be obtained by reacting a compound having

OCN-R ₁ -NCO general formula (I)

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

In the general formulas (III-1) to (III-3), R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ may be the same or different from each other, and may be divalent aliphatic. Or represents an 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 arylene group having 6 to 15 carbon atoms, and an alkylene or carbon number having 2 to 10 carbon atoms. 6 to 10 arylene groups are more preferred. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. preferable. In addition, in R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups, There may be an amide group, a ureido group, or a halogen atom.

In General 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. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ˜6 alkyl and aryl groups having 6 to 10 carbon atoms. R ₁₂ may contain other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms. m represents an integer of 2 to 4.

In General Formula (III-5), R ₁₃ represents an aryl group or a cyano group, and preferably an aryl group or a cyano group having 6 to 10 carbon atoms.
In the general formulas (III-1) to (III-6), n ₁ , n ₂ , n ₃ , n ₄ , n ₅ , n ₇ , n ₈ and n ₉ each represents an integer of 2 or more. , An integer of 2 to 100 is preferable. In General Formula (III-5), n ₆ represents 0 or an integer of 2 or more, and 0 or an integer of 2 to 100 is preferable.

In General Formulas (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 1 to 1 carbon atoms. 10 hydrocarbon groups are represented. p represents 0 or an integer of 1 to 10.

Incidentally, when reacted with a compound having an epoxy group or an oxetane group in the carboxyl group-containing polyurethane and the molecule, X, the partial structure Y or Z is linked to the polyurethane backbone, -CO 2 - _{(beta-position} or γ-position It has a structure having an aliphatic group)-(*) substituted with a hydroxyl group or an acyloxy group. Here, the partial structures of the general formulas (1) to (3) exist on the (*) side.

The polyurethane resin (ii) may further be copolymerized with a carboxyl group-free low molecular weight diol as a fifth component. Examples of the low molecular weight diol compound include those represented by the general formulas (III-1) to (III) III-6) having a mass average molecular weight of 500 or less. The carboxyl group-free low molecular weight diol can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.
As said low molecular weight diol compound, the compound described in the paragraph [0048] of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned, for example.

  As the polyurethane resin (ii), in particular, the diisocyanate represented by the general formula (I) and at least one selected from the carboxyl group-containing diols represented by the above formulas (17) to (19) are essential. As a component, depending on the purpose, at least one selected from polymer diols having a weight average molecular weight of 800 to 3,000, represented by general formulas (III-1) to (III-6), A reaction product with a low molecular weight diol having a mass average molecular weight of 500 or less and represented by formulas (III-1) to (III-6) is further added to the general formulas (IV-1) to (IV-16). The acid value obtained by reacting a compound having one epoxy group and at least one (meth) acrylic group in the molecule represented by any one of the following, is 20 mg KOH / g to 120 mg KOH / An alkali-soluble photocrosslinkable polyurethane resin g is preferred.

  In addition, also in the said polyurethane resin (ii), it replaced with the compound represented by the said general formula (III-1)-(III-6), or used together, and the general demonstrated by the above-mentioned polyurethane resin (i). It is preferable to use the diol compound represented by the formula (U), and the mass ratio of the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is the above-mentioned polyurethane. The same as in the case of the resin (i).

  These high molecular compounds may be used individually by 1 type, and may use 2 or more types together.

Also in the polyurethane resin (ii), those having at least one carboxyl group at the terminal of the polymer main chain are preferable for obtaining the same effect as the polyurethane resin (i), and are described in the polyurethane resin (i). The terminal block method of the polymer main chain and the group represented by the general formula (A) are preferable, and the preferable range is the same as that of the polyurethane resin (i).

  Examples of the polyurethane resin (ii) include epoxy group and vinyl group-containing compounds in polymers U1 to U4 and U6 to U11 shown in paragraphs [0314] to [0315] of JP-A-2007-2030. Glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400, Daicel Chemical Corporation) Polymer) in place of (manufactured).

—Synthesis Method of Polyurethane Resin (ii) Obtained by Reacting Carboxyl Group-Containing Polyurethane with Compound Having Epoxy Group and Ethylenically Unsaturated Group in the Molecule—
As a method for synthesizing the polyurethane resin (ii), the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, the molar ratio of the diisocyanate and diol compound can be determined by treating with an alcohol or an amine. In the form in which no isocyanate group remains.

<Acid-modified ethylenically unsaturated group-containing epoxy resin>
In the present invention, an acid-modified ethylenically unsaturated group-containing epoxy resin is used together with the acid-modified ethylenically unsaturated group-containing polyurethane resin.
The acid-modified ethylenically unsaturated group-containing epoxy resin used in the present invention has a partial structure represented by the following general formula (EP).

In the general formula (EP), one of R ^A1 and R ^A2 represents an unsaturated aliphatic group, and the other represents a saturated or unsaturated aliphatic group having a carboxyl group or an aromatic group having a carboxyl group. Represent. R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom or a substituent.

The partial structure represented by the general formula (EP) is obtained by a reaction of (a) an epoxy resin, (b) an unsaturated group-containing monocarboxylic acid, and (c) a polybasic acid anhydride.
That is, the unsaturated aliphatic group in the general formula (EP) is a group derived from an unsaturated group-containing monocarboxylic acid, and is a group obtained by removing —COOH from this unsaturated group-containing monocarboxylic acid. . On the other hand, a saturated or unsaturated aliphatic group having a carboxyl group or an aromatic group having a carboxyl group is a group obtained from a polybasic acid anhydride, and is, for example, a group in a square frame described below.

As the unsaturated aliphatic group in the general formula (EP), —C (R ¹ ) = C (R ² ) (R in the general formula (1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin described above. ³ ) is preferred. Here, R < ¹ > -R < ³ > is synonymous with R < ¹ > -R < ³ > in the said General formula (1), and its preferable range is also the same.
Examples of the unsaturated aliphatic group include vinyl group, α-methylvinyl group, β-methylvinyl group, β-furfurylvinyl group, β-styrylvinyl group, β-phenylvinyl group, α-cyano-β. -A phenyl vinyl group and a 1, 3-pentadienyl group are mentioned.
Examples of the unsaturated group-containing monocarboxylic acid in (b) above include, for example, acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, Crotonic acid, α-cyanocinnamic acid, sorbic acid, and the like can be used. Also, half-ester compounds, unsaturated group-containing monoglycidyl ethers or unsaturated group-containing monoglycidyl esters and saturated or unsaturated group-containing products, which are reaction products of hydroxyl group-containing acrylates and saturated or unsaturated group-containing dibasic acid anhydrides A half-ester compound which is a reaction product with a dibasic acid anhydride can be used. Here, the half ester compound refers to, for example, a compound in which only one of two carboxyl groups is esterified. These (b) unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.

  The half ester compound is obtained by reacting a hydroxyl group-containing acrylate, an unsaturated group-containing monoglycidyl ether or an unsaturated group-containing monoglycidyl ester, and a saturated or unsaturated group-containing dibasic acid anhydride in an equimolar ratio. Can do.

Examples of the hydroxyl group-containing acrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, and trimethylol. Propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycidyl acrylate, glycidyl methacrylate, and the like can be used.
As the unsaturated group-containing monoglycidyl ether or unsaturated group-containing monoglycidyl ester, glycidyl (meth) acrylate or the like can be used.

  As the saturated or unsaturated aliphatic group having a carboxyl group or the aromatic group having a carboxyl group in the general formula (EP), examples of the saturated or unsaturated aliphatic group having a carboxy group include an alkyl group, an alkenyl group, Examples include a cycloalkyl group, a cycloalkenyl group, and an aryl group substituted with a carboxyl group. Examples of the aromatic group having a carboxy group include a phenyl group substituted with a carboxyl group.

  Examples of polybasic acid anhydrides include saturated or unsaturated group-containing dibasic acid anhydrides such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyl Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like can be used.

R ^{EP1 to} R ^EP3 in the general formula (EP) each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

  The acid-modified ethylenically unsaturated group-containing epoxy resin in the present invention is preferably an epoxy resin represented by any one of the following general formulas (P1) to (P3).

In the general formulas (P1) to (P3), R ^e1 represents a group represented by the general formula (EP) or an epoxy group. R ^e3 represents a hydrogen atom or a methyl group. R ^e3 and ^e3 each independently represent a hydrogen atom, an alkyl group or an aryl group. n ^{e1 to} n ^e3 each independently represents a number of 1 or more. However, R ^e1 is not ^{entirely an} epoxy group in the molecule. Further, a plurality of R ^e1 present in the molecule may be the same or different from each other, a plurality of R ^e3 to R ^e5 present in the molecule may be the same or different from each other. Y represents —O—, —C (═O) —O—, —O—C (═O) — or —N (Rx) —. Here, Rx represents a hydrogen atom or a monovalent organic group. La is an alkylene group or ^a divalent group having —O—, —C (═O) —O—, —O—C (═O) — or —O—C (═O) —O— in the linking chain. Represents a linking group. L ^b represents a divalent linking group having at least an alkyl partial structure, a cycloalkyl partial structure, or an aryl partial structure. L ^c and L ^d each independently represent a divalent linking group.

As the monovalent organic group in Rx, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, and a sulfamoyl group are preferable, and an alkyl group, an aryl group, and a heterocyclic group are more preferable. .
La is an alkylene group or ^a divalent group having —O—, —C (═O) —O—, —O—C (═O) — or —O—C (═O) —O— in the linking chain. The divalent group other than the alkylene group is at least —O—, —C (═O) —O—, —O—C (═O) — or —O in the linking chain. Any divalent linking group may be used as long as it has —C (═O) —O—, but —O—, —C (═O) —O—, —O—C (═O) may be used. In addition to —, —O—C (═O) —O—, an alkylene group, a phenylene group, a divalent heterocyclic group, or a group that combines an alkylene group, a phenylene group, and a divalent heterocyclic group is preferable. More preferred is —O—, —C (═O) —O—, —O—C (═O) —, —O—C (═O) —O— alone or a combination thereof.

L ^b represents a divalent linking group having at least an alkyl partial structure, a cycloalkyl partial structure or an aryl partial structure, and is preferably an alkylene group and an arylene group or a combination thereof. Examples of the cycloalkylene group include cyclopentanediyl, cyclohexanediyl, and dicyclopentanediyl, and the alkylene group is preferably —C (Ry) (Ry ′) —. Here, Ry and Ry ′ each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Among them, —CH ₂ —, —CH (CH ₃ ) —, and —C (CH ₃ ) ₂ — are preferable as the alkylene group.
The divalent linking group in L ^c and L ^d includes an alkylene group, an arylene group, a divalent heterocyclic group, —O—, —S—, —C (═O) —, —N (Rx) —, and these Are preferred. Here, Rx represents a hydrogen atom or a substituent.

  The acid-modified ethylenically unsaturated group-containing epoxy resin represented by any one of (P1) to (P3) is an epoxy represented by any one of the following general formulas (P1-1) to (P3-1). A resin is preferred.

In the general formulas (P1-1) to (P3-1), R ^e1 represents a group represented by the general formula (EP) or an epoxy group. R ^e2 and R ^e3 each independently represent a hydrogen atom or a methyl group, and R ^{e4 to} R ^e9 each independently represent a hydrogen atom, an alkyl group, or an aryl group. n ^e1 and n ^e2 each independently represent a number of 1 or more, and n ^e3 represents 0 or a number of 1 or more. However, R ^e1 is not ^{entirely an} epoxy group in the molecule. A plurality of R ^e1 present in the molecule may be the same or different, and a plurality of R ^e2 and R ^e3 present in the molecule may be the same or different. In R ^{e4 to} R ^e9 , each of the plurality of R ^{e4 to} R ^e9 present in the molecule may be the same as or different from each other.

Among the epoxy resins represented by the general formulas (P1-1) to (P3-1), in the present invention, an epoxy resin represented by the general formula (P2-1) or (P3-1) is preferable. The epoxy resin represented by Formula (P3-1) is more preferable.
The acid-modified ethylenically unsaturated group-containing epoxy resin used in the present invention has the same molecular weight, acid value, and ethylenically unsaturated group equivalent as the acid-modified ethylenically unsaturated group-containing polyurethane resin used in the present invention. It is preferable.

-Content of acid-modified ethylenically unsaturated group-containing urethane resin and acid-modified ethylenically unsaturated group-containing epoxy resin-
Of the acid-modified ethylenically unsaturated group-containing urethane resin in the total mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the acid-modified ethylenically unsaturated group-containing epoxy resin in the photosensitive composition There is no restriction | limiting in particular as a ratio, Although it can select suitably according to the objective, 55 mass%-95 mass% are preferable, and 65 mass%-75 mass% are more preferable. When the ratio is less than 55% by mass, the thermal shock resistance may be lowered, and when it exceeds 95% by mass, the insulation may be lowered. When the ratio is within the more preferable range, it is advantageous in that both insulation and thermal shock resistance are very excellent.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has one or more functional groups which have an ethylenically unsaturated group is preferable.

  Examples of the functional group having an ethylenically unsaturated group include a (meth) acryloyl group, a (meth) acrylamide group, a vinylphenyl group, a vinyl ester group, a vinyl ether group, an allyl ether group, and an allyl ester group.

  There is no restriction | limiting in particular as a compound which has one or more functional groups which have the said ethylenically unsaturated group, Although it can select suitably according to the objective, At least 1 selected from the monomer which has a (meth) acryl group. Species are preferred.

There is no restriction | limiting in particular as a monomer which has the said (meth) acryloyl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dicyclopentane dimethylol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate , Trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanate Nurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; a polyfunctional alcohol such as trimethylolpropane, glycerin, bisphenol and (meth) acrylate after addition reaction of ethylene oxide or propylene oxide; Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentane dimethylol di (meth) acrylate, Tricyclodecane dimethanol (meth) acrylate is more preferred.
As the polymerizable compound, compounds having an alicyclic ring such as those having two or more acryloyloxy groups and methacryloyloxy groups and tricyclodecane dimethanol (meth) acrylate are preferable.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said polymeric compound, Although it can select suitably according to the objective, 5 mass%-50 mass% are preferable, and 10 mass%- 40 mass% is more preferable. When the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Those having photosensitivity are preferable, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of monomer. May be.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.
As said photoinitiator, a neutral photoinitiator is preferable. Moreover, the other photoinitiator may be included as needed.

  The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a compound having at least an aromatic group, such as (bis) acylphosphine oxide or an ester thereof. More preferred are acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds. Two or more neutral photopolymerization initiators may be used in combination.

  Examples of the photopolymerization initiator include (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, and thiols. Compound etc. are mentioned. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, oxime derivatives, (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone Compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.

  Examples of the (bis) acylphosphine oxide, the acetophenone compound, the benzophenone compound, the benzoin ether compound, the ketal derivative compound, and the thioxanthone compound include, for example, paragraph [0042] of JP 2010-256399 A Examples thereof include (bis) acylphosphine oxides, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds.

  Examples of the oxime derivative include oxime derivatives described in paragraphs [0043] to [0059] of JP2010-256399A.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0 More preferably, the content is more preferably 5% by mass to 20% by mass, and particularly preferably 0.5% by mass to 15% by mass.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. An epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), an oxetane compound having at least two oxetanyl groups in one molecule can be used, and is described in JP-A-2007-47729. A compound obtained by reacting a blocking agent with an isocyanate group of an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate or a derivative thereof ( Blocked polyisocyanate compound).

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

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 3 mass%- 30 mass% is more preferable. If the said content is 1 mass% or more, the film | membrane intensity | strength of a cured film will be improved, and if it is 50 mass% or less, developability and exposure sensitivity will become favorable.

  Examples of the epoxy compound include epoxy compounds described in paragraphs [0071] to [0073] of JP2010-256399A.

  Examples of the oxetane compound include oxetane compounds described in paragraph [0074] of JP2010-256399A.

  Examples of the polyisocyanate compound include the polyisocyanate compounds described in paragraph [0075] of JP2010-256399A.

  Examples of the blocked polyisocyanate compound include the blocked polyisocyanate compound described in paragraph [0076] of JP2010-256399A.

  Examples of the melamine derivative include melamine derivatives described in paragraph [0077] of JP 2010-256399 A.

<Flame Retardant>
The photosensitive composition of the present invention preferably contains a flame retardant.
Examples of flame retardants include phosphorus compounds, brominated compounds such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, and chlorinated compounds such as chlorinated paraffin. However, phosphorus compounds are preferred.
<Phosphorus-containing flame retardant>
Examples of phosphorus-containing flame retardants include condensed phosphoric acid compounds, polyphosphoric acid melamine salts, phosphazene compounds, and organic phosphinic acid metal salts. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the condensed phosphoric acid compound include resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and commercially available products can be used. Examples of the commercially available products include CR-733S. , CR-741, CR-747, PX-200 (manufactured by Daihachi Chemical Co., Ltd.), FP-600, FP-700 (manufactured by Adeka), Reofos RDP, Reofos BAPP (manufactured by Ajinomoto Fine Techno Co., Ltd.) ), Etc.

  As a polyphosphate melamine salt, it is a compound represented, for example by the following general formula, and n represents the number of 1 or more. Commercial products can be used. As this commercial item, AP750, AP760, OP1312 (above, Clariant Japan company make), FP-2100J, FP-2200 (above, made by Adeka company), Hishiguard 6ME (Nihon Chemical Industry Co., Ltd. make), FCP-770 (Suzuhiro Chemical Co., Ltd.).

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

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

In the present invention, an organic phosphinic acid metal salt is preferred.
5 mass%-35 mass% are preferable, and, as for content in the said photosensitive composition solid content of a phosphorus containing flame retardant, 5 mass%-30 mass% are more preferable. When the content is less than 5% by mass, sufficient flame retardancy may not be maintained. When the content exceeds 35% by mass, resolution is deteriorated, folding resistance is deteriorated, and insulation reliability is deteriorated. It may become.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a filler, a thermosetting accelerator, a thermal-polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye) etc. Furthermore, adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, A chain transfer agent or the like) may be used in combination.
By appropriately containing these components, properties such as stability, photographic properties, and film properties of the intended photosensitive composition can be adjusted.
By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.
Examples of the filler include paragraphs [0098] to [00099] of JP-A-2008-250074.
In the present invention, in order to effectively exhibit the effects of the present invention, it is preferable that the photosensitive composition does not contain inorganic fine particles which are inorganic fillers, and even if contained, the solid content ratio of the photosensitive composition And less than 15% by mass, preferably 5% by mass or less.
Examples of the thermal polymerization inhibitor include thermal polymerization inhibitors described in paragraphs [0101] to [0102] of JP-A-2008-250074.
Examples of the thermosetting accelerator include the thermosetting accelerator described in paragraph [0093] of JP-A-2008-250074.
Examples of the plasticizer include the plasticizers described in paragraphs [0103] to [0104] of JP-A-2008-250074.
Examples of the colorant include the colorants described in paragraphs [0105] to [0106] of JP-A-2008-250074.
Examples of the adhesion promoter include adhesion promoters described in paragraphs [0107] to [0109] of JP-A-2008-250074.

  There is no restriction | limiting in particular as a usage form of the said photosensitive composition, According to the objective, it can select suitably, You may use it in a liquid state and may use it as a photosensitive film.

(Photosensitive dry film)
The photosensitive dry film of the present invention has at least a carrier film (support film) and a photosensitive layer containing the photosensitive composition of the present invention on the carrier film, and, if necessary, other layers. Have

<Carrier film>
The carrier film is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.
There is no restriction | limiting in particular as a carrier film, According to the objective, it can select suitably, For example, the support body as described in Paragraph [0115]-[0117] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

<Photosensitive layer>
If the said photosensitive layer is a layer containing the said photosensitive composition of this invention, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.

  As the method for forming the photosensitive layer, for example, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support. The method of laminating | stacking by apply | coating directly and drying is mentioned.

  There is no restriction | limiting in particular as a solvent used for the said photosensitive composition solution, According to the objective, it can select suitably.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating etc. are mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

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

<Other layers>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, etc. Layer. The said photosensitive dry film may have these layers individually by 1 type, and may have 2 or more types.

-Protective film-
The photosensitive film may form a protective film on the photosensitive layer.
There is no restriction | limiting in particular as said protective film, According to the objective, it can select suitably, For example, the protective film as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.
There is no restriction | limiting in particular as a combination of the said protective film and the said support body, According to the objective, it can select suitably, For example, the combination as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned. It is done.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

  The length and storage method of the photosensitive dry film are not particularly limited and can be appropriately selected depending on the purpose. For example, the length described in paragraph [0120] of JP-A-2008-250074, Examples include storage methods.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying it at 30 to 150 ° C. for 1 to 30 minutes. As for the temperature in the case of the said drying, 50 to 120 degreeC is especially preferable.

(Photosensitive laminate)
The photosensitive laminate of the present invention comprises at least a substrate and a photosensitive layer on the substrate, and further laminates other layers as necessary.
The photosensitive layer is a layer containing the photosensitive composition of the present invention.
The photosensitive layer is, for example, transferred from the photosensitive dry film produced by the above-described manufacturing method, and has the same configuration as described above.

<Base material>
The substrate (substrate) is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited. For example, a material having a high surface smoothness to a material having an uneven surface can be arbitrarily selected, but a plate-like base material, a so-called substrate is preferable. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, etc. In the present invention, polyimide film is used. Particularly preferred.

<Method for producing photosensitive laminate>
The method for producing the photosensitive laminate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of heating and pressing at least the photosensitive layer in the photosensitive dry film of the present invention. For example, a method of transferring and laminating while performing.

An example of the manufacturing method of the said photosensitive laminated body is the method of laminating | stacking the photosensitive film of this invention on the surface of the said base | substrate, performing at least any one of a heating and pressurization. In addition, when the said photosensitive dry film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator Co., Ltd. make, VP-II, Nichigo Morton Co., Ltd. make, VP130) is preferable.

  The photosensitive dry film and the photosensitive laminate of the present invention can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and are preferably used for forming a permanent pattern of a printed circuit board, particularly a flexible wiring board. be able to.

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

<Exposure process>
The exposure step is not particularly limited as long as it is a step of exposing the photosensitive layer formed of the photosensitive composition of the present invention, and can be appropriately selected according to the purpose. The process etc. which expose with respect to the photosensitive layer in the said photosensitive laminated body are mentioned.

  The exposure target is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. However, at least one of heating and pressurizing the photosensitive dry film on the substrate is performed. However, it is preferably performed on a laminate formed by laminating.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, For example, digital exposure, analog exposure, etc. are mentioned.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.

-Development process-
The developing step is a step of removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as a removal method of the said exposed part, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, the developing solution as described in Paragraph [0171]-[0173] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

  The method for the entire surface exposure treatment and the entire surface heat treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, in paragraphs [0176] to [0177] of JP-A-2008-250074 The method of description is mentioned.

In the case where the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, on a printed circuit board, particularly on a flexible wiring board in the present invention. A permanent pattern can be formed by the permanent pattern forming method, and soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), a solder resist, particularly a flexible solder resist, and prevents external impact and conduction between adjacent electrodes. The

(Printed board)
A printed wiring board, particularly a flexible wiring board that is preferable in the present invention, includes at least a base and a permanent pattern formed by the permanent pattern forming method, and further, other electronic members appropriately selected as necessary. Have

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples at all. In the examples, “part” represents “part by mass”.

In addition, the acid value and mass average molecular weight in the preparation examples were measured by the following methods.
<Acid value>
The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
<Mass average molecular weight>
The mass average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.). That is, 0.5% by mass of THF (tetrahydrofuran) solution was used as the sample solution, the column used was one TSKgel HZM-M, 200 μL of sample was injected, eluted with the THF solution, and the refractive index at 25 ° C. Measured with a detector. Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.

(Preparation Example 1)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU1>
To a 1 L three-necked round bottom flask equipped with a condenser and a stirrer was added 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA) and 35.44 g of glycerol monomethacrylate (GLM). (0.221 mol), 78.75 g (0.079 mol) of polypropylene glycol (molecular weight 1000) (PPG1000) and 6.03 g (0.045 mol) of malic acid were dissolved in 300 mL of cyclohexanone. To this, 23.46 g (0.094 mol) of 4,4-diphenylmethane diisocyanate (MDI), 47.30 g (0.281 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene 0 As a catalyst, 0.6 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) was added and stirred at 75 ° C. for 5 hours. After cooling to room temperature, the concentration was adjusted with cyclohexanone to obtain an acid-modified ethylenically unsaturated group-containing polyurethane resin (PU1) solution having a solid concentration of 40% by mass.
The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin (PU1) had a mass average molecular weight of 7,000, a solid content acid value of 46 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.1 mmol / g. .

(Preparation Example 2)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU2>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined with 15.00 g (0.101 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). , 31.83 g (0.199 mol) of glycerol monomethacrylate (GLM), 75 g (0.075 mol) of polytetramethylene glycol (molecular weight 1000) (PTMG1000) and 6.03 g (0.045 mol) of malic acid The solid content concentration is 40 quality in the same manner as in Preparation Example 1 except that % Acid modified ethylene unsaturated group-containing polyurethane resin (PU2) to obtain a solution.
The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin (PU2) had a mass average molecular weight of 8,600, a solid content acid value of 54 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.0 mmol / g. .

(Preparation Example 3)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU3>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined with 15.00 g (0.101 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). Glycerol monomethacrylate (GLM) 31.83 g (0.199 mol), polylite OD-X-240 (DIC Corporation, molecular weight 1000) 75 g (0.075 mol) and malic acid 6.03 g (0.045 mol) ), Except that the combination was changed to a solid content concentration of 40% by mass in the same manner as in Preparation Example 1. Acid modified ethylene unsaturated group-containing polyurethane resin (PU3) to obtain a solution.
The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin (PU3) had a mass average molecular weight of 8,300, a solid content acid value of 54 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.0 mmol / g. .

(Preparation Example 4)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU4>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined with 15.00 g (0.101 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). Glycerol monomethacrylate (GLM) 31.83 g (0.199 mol), ETERNACOL UH-100 (manufactured by Ube Industries, molecular weight 1000) 75 g (0.075 mol) and malic acid 6.03 g (0.045 mol) The solid content concentration was 40% by mass in the same manner as in Preparation Example 1 except that the combination was changed. An acid-modified ethylenically unsaturated group-containing polyurethane resin (PU4) solution was obtained.
The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin (PU4) had a mass average molecular weight of 8,800, a solid content acid value of 54 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.0 mmol / g. .

(Preparation Example 5)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU5>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined with 22.22 g (0.15 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). Preparation Example, except that the combination was changed to 27.63 g (0.173 mol) of glycerol monomethacrylate (GLM) and 52.5 g (0.053 mol) of ETERNACOL UH-100 (manufactured by Ube Industries, molecular weight 1000) 1 and acid-modified ethylenically unsaturated group-containing polyurea having a solid concentration of 40% by mass A tan resin (PU5) solution was obtained.
The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin (PU5) had a mass average molecular weight of 16,500, a solid content acid value of 50 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.0 mmol / g. .

(Preparation Example 6)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU6>
In Preparation Example 1, a combination of 23.46 g (0.094 mol) of 4,4-diphenylmethane diisocyanate (MDI) and 47.30 g (0.281 mol) of hexamethylene diisocyanate (HMDI) was added to 66.68 g (0 .3 mol) and 12.61 g (0.075 mol) of hexamethylene diisocyanate (HMDI) in the same manner as in Preparation Example 1, except that the acid-modified ethylenic acid having a solid content concentration of 40% by mass is used. A saturated group-containing polyurethane resin (PU6) solution was obtained.
The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin (PU6) had a mass average molecular weight of 9,200, a solid content acid value of 45 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.05 mmol / g. .

(Preparation Example 7)
<Preparation of acid-modified ethylenically unsaturated group-containing polyurethane resin PU7>
In Preparation Example 1, a combination of 23.46 g (0.094 mol) of 4,4-diphenylmethane diisocyanate (MDI) and 47.30 g (0.281 mol) of hexamethylene diisocyanate (HMDI) was converted into 4,4-diphenylmethane diisocyanate ( MDI) An acid-modified ethylenically unsaturated group-containing polyurethane resin (PU7) solution having a solid content concentration of 40% by mass was obtained in the same manner as in Preparation Example 1, except that 93.85 g (0.375 mol) was used. .
The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin (PU7) has a weight average molecular weight of 9,000, a solid content acid value of 41.1 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.98 mmol / g. there were.

(Adjustment examples 8 to 14)
In the same manner as in Adjustment Example 1, except that the diurethane compound and diol compound listed in Table 1 below were changed to the stated molar ratios and the reaction time was changed to 7 hours, the same as in Adjustment Example 1, solid content concentration of 40 Each solution of the mass% acid-modified ethylenically unsaturated group-containing polyurethane resins (PU8) to (PU14) was obtained.
In Table 1, the repeating unit incorporated in the polymer is described as the binder structural formula, but the raw materials used in the preparation are a diurethane compound and a diol compound.

(Preparation Example 15)
<Preparation of acid-modified ethylenically unsaturated group-containing epoxy resin PE5>
In a reaction vessel equipped with a gas introduction tube, a stirrer, a cooling tube, a thermometer, and a dropping funnel for continuous dropping, 86 parts by mass of 1,4-cyclohexanedicarboxylic acid having a carboxylic acid equivalent of 86 g / equivalent and a bisphenol A type epoxy resin (Japan) 378 parts by mass of Epoxy Resin Co., Ltd., Epicoat 828, Epoxy equivalent 189 g / equivalent) were charged and dissolved at 110 ° C. under stirring in a nitrogen atmosphere. Thereafter, 0.3 part by mass of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., and the reaction was allowed to proceed for about 90 minutes while maintaining the temperature at 150 ° C. to obtain an epoxy equivalent of 464 g / equivalent epoxy compound. Got. Next, the temperature in the flask was cooled to 40 ° C., 390 parts by mass of carbitol acetate was added and dissolved by heating, 0.46 parts by mass of methylhydroquinone and 1.38 parts by mass of triphenylphosphine were added, and 95 to 105 ° C. Then, 72 parts by mass of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 190 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. The resin solution thus obtained had a solid acid value of 100 mgKOH / g. Then, it diluted with carbitol acetate so that solid content concentration might be 40 mass%, and the acid-modified ethylenically unsaturated group containing epoxy resin (PE5) solution was obtained.

(Preparation Example 16)
<Preparation of acid-modified ethylenically unsaturated group-containing epoxy resin PE6>
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy Equivalent 220) 660 g, carbitol acetate 421.3 g, and solvent naphtha 180.6 g were introduced, heated and stirred at 90 ° C., and dissolved. Next, it is once cooled to 60 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g. Got. This was charged with 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for 6 hours. As a result, a solution of a carboxyl group-containing resin having an acid value of 50 mgKOH / g, an ethylenically unsaturated group (g mass of resin per 1 mol of double bond unsaturated group), and a mass average molecular weight of 7,000 was obtained. Then, it diluted with carbitol acetate so that solid content concentration might be 40 mass%, and the acid-modified ethylenically unsaturated group containing epoxy resin (PE6) solution was obtained.

(Preparation Example 17)
<Preparation of acid-modified ethylenically unsaturated group-containing epoxy resin PE7>
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 450 g of epoxy resin (DIC Corporation, EXA-4850-150, epoxy equivalent 450), carbitol acetate 430 g was introduced, heated and stirred to dissolve. Next, it is once cooled to 60 ° C., 72 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g. Got. This was charged with 122 g of tetrahydrophthalic anhydride, heated to 90 ° C., and reacted for 6 hours. As a result, a solution of a carboxyl group-containing resin having an acid value of 70 mgKOH / g and a crosslinking group equivalent of 1.55 mmol / g was obtained. Then, it diluted with carbitol acetate so that solid content concentration might be 40 mass%, and the acid-modified ethylenically unsaturated group containing epoxy resin (PE7) solution was obtained.

(Preparation Example 18)
<Preparation of acid-modified ethylenically unsaturated group-containing epoxy resin PE8>
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 260 g of novolak type epoxy resin (manufactured by DIC, HP-7200, epoxy equivalent 260), carbitol acetate 303 g was introduced, heated and stirred to dissolve. Next, it is once cooled to 60 ° C., 72 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g. Got. This was charged with 122 g of tetrahydrophthalic anhydride, heated to 90 ° C., and reacted for 6 hours. As a result, a solution of a carboxyl group-containing resin having an acid value of 100 mgKOH / g and a crosslinking group equivalent of 2.19 mmol / g was obtained. Then, it diluted with carbitol acetate so that solid content concentration might be 40 mass%, and the acid-modified ethylenically unsaturated group containing epoxy resin (PE8) solution was obtained.

(Preparation example a)
<Preparation of organophosphinic acid metal salt dispersion>
13.13 parts by mass of an organic phosphinic acid metal salt (trade name: OP-935, manufactured by Clariant Japan) and a specific mixed solution of each resin prepared in each of the above preparation examples (solid content concentration 40% by mass) 75.40 A motor in which 0.66 parts by mass of a dispersant, 0.66 parts by mass of a dispersant (trade name: BYK-W903, manufactured by Big Chemie Japan) and 10.82 parts by mass of cyclohexanone were weighed and filled with zirconia beads having a diameter of 0.65 mm. An organic phosphinic acid metal salt dispersion in which an organic phosphinic acid metal salt having an average particle size of 0.1 μm and a maximum particle size of 2 μm was dispersed in a resin was obtained by dispersing using a Mill M-50 (manufactured by Eiger). .

The average particle size and the maximum particle size were measured by the following methods.
A solution obtained by diluting the organophosphinic acid metal salt dispersion by a factor of 50 was measured using a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement principle was a dynamic light scattering method, and the size distribution analysis method was measured as a cumulant method and / or a histogram method.
The average particle size is defined as a particle size of an integrated value of 50% when expressed as an integrated (cumulative) mass percentage, and is defined as d50 (D50), and the maximum particle size is an integrated value of 100%. And is defined as d100 (D100) or the like.

Example 1
<Manufacture of photosensitive film>
On a 16 μm thick polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) as a support, a photosensitive composition solution having the following composition is applied and dried to form a 30 μm thick photosensitive layer on the support. did. On the photosensitive layer, a 20 μm-thick polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated as a protective layer to produce a photosensitive film.

-Composition of photosensitive composition solution-
-Organic phosphinic acid metal salt dispersion liquid of Preparation Example a above-54.42 parts by mass-Polymerizable compound (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)-8.96 parts by mass-Thermal crosslinking agent (Epototo YDF) -170, manufactured by Tohto Kasei Co., Ltd.) ... 9.77 parts by mass
(Bisphenol F type epoxy resin)
-Acid-modified ethylenically unsaturated group-containing resin (solid content concentration 40% by mass) ... 13.68 parts by mass (polyurethane resin PU1 and epoxy resin ZFR-1492H (manufactured by Nippon Kayaku))
・ Irgacure 907 0.98 parts by mass EAB-F (Hodogaya Chemical Co., Ltd.) 0.033 parts by mass DETX-S (Nippon Kayaku Co., Ltd.) 0.009 parts by mass Pigment Dispersion (hereinafter referred to as “G-1”).

The pigment dispersion “G-1” is 0.42 parts by mass of phthalocyanine blue, 0.12 parts by mass of anthraquinone yellow pigment (CI PY24), 12.85 parts by mass, and 86.62 of cyclohexanone. After mixing with the mass part in advance, it was prepared by dispersing for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm with a motor mill M-250 (manufactured by Eiger).
Moreover, in the said photosensitive composition, the total mass (total mass of solid content) of acid-modified ethylenically unsaturated group containing urethane resin PU1 and acid-modified ethylenically unsaturated group containing epoxy resin ZFR-1492H (made by Nippon Kayaku). The ratio of the solid mass of the acid-modified ethylenically unsaturated group-containing urethane resin PU1 is 90% by mass.

-Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through holes, copper thickness 12 μm) to chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were as follows: vacuuming time 40 seconds, pressure bonding temperature 70 ° C., pressure bonding pressure 0.2 MPa, and pressure time 10 seconds.

-Exposure process-
A predetermined pattern is obtained with a parallel light exposure machine (ultra-high pressure mercury lamp) from the polyethylene terephthalate film (support) side through a glass mask having a predetermined pattern with respect to the photosensitive layer in the prepared photosensitive laminate. Irradiation was performed with an energy amount of 60 mJ / cm ² to cure a part of the photosensitive layer.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1% by mass sodium carbonate aqueous solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Was spray-developed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the laminate on which the permanent pattern is formed is subjected to a heat treatment at 150 ° C. for 1 hour, and then subjected to post-exposure under the condition of 1 J / cm ² to cure the surface of the permanent pattern and to improve the film strength. Raised and produced a test plate.

  Insulation, folding resistance, resolution and flame retardancy were evaluated as follows. The results are shown in Tables 2 to 5 below.

<Insulation (HHBT)>
In the lamination to the substrate, the copper-clad laminate was laminated to the substrate in the same manner as above except that the copper thickness was changed to a comb-shaped substrate having a copper thickness of 12 μm and L (line) / S (space) = 25 μm / 25 μm. An exposure process, a development process, and a curing process were performed to produce a substrate for evaluation.
Using the evaluation substrate, a super accelerated high temperature high humidity life test (HAST) was performed under the conditions of 130 ° C., 85% RH, 50 V, 200 hours.
Thereafter, the degree of migration of solder resist on the evaluation substrate was observed with a 100 × optical microscope.
〔Evaluation criteria〕
A: No short circuit. Furthermore, the occurrence of migration cannot be confirmed, and the insulation is excellent. B: No short circuit. However, the occurrence of migration is slightly confirmed on copper. C: There is a short circuit. The occurrence of migration is confirmed slightly on copper. D: There is a short circuit. The occurrence of migration is also confirmed

<Folding resistance>
A dry film resist is laminated to a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series) in which a copper foil (copper foil thickness 18 μm) is laminated on a polyimide base material (polyimide thickness 25 μm), and 18 mJ After exposure at / cm ² , development was performed under the condition of 0.15 MPa / 40 s to produce a line pattern of L / S = 100/100 μm. After etching the substrate for flexible printed wiring board to which the line pattern of the dry film resist is applied, the dry film resist is peeled off by 3% by mass aqueous sodium hydroxide / 0.1 MPa / 120 s, so that L / S = 100 A wiring pattern of / 100 μm was created.
Then, the photosensitive layer of the prepared photosensitive film was laminated on the wiring pattern side to the obtained polyimide with a wiring pattern and allowed to stand at room temperature for 10 minutes, and then irradiated with an energy amount of 150 mJ / cm ² with an ultra-high pressure mercury lamp. Expose and harden the photosensitive layer, heat treatment at 160 ° C. for 1 hour, and then irradiate with exposure to an energy amount of 1,000 mJ / cm ² to cure the photosensitive layer and increase the film strength. Thus, a laminate for evaluation was obtained.
The obtained laminate for evaluation was cut into 5 mm × 10 cm squares, bent 180 ° in the long side direction with the wiring pattern on the outside, a predetermined weight was placed on the bent part for 3 seconds, and the folding resistance was evaluated according to the following criteria. .
〔Evaluation criteria〕
A: 400 g with no crack B: 200 g with no crack C: 200 g with a crack length of 10% or less of the bent side length D: 200 g with a crack length of the bent side length More than 10%

<Resolution>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, a round hole pattern is used to form a round hole with a diameter of 30 μm to 100 μm at a diameter of 60 mJ / cm using a pattern forming apparatus. ² was exposed.
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve and remove uncured areas. did.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and there is no abnormality such as pattern residue, undercut, or peeling, and the smallest round hole pattern that can form a space The width was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution.
〔Evaluation criteria〕
A: A round hole with a diameter of 50 μm or less can be resolved and has excellent resolution. B: A round hole with a diameter exceeding 50 μm and not more than 70 μm can be resolved, and the resolution is good C: 70 μm in diameter Can be resolved, and the resolution is slightly inferior. D: The round hole cannot be resolved, and the resolution is inferior.

<Flame retardance>
Etching a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series), which is made by laminating a copper foil (copper foil thickness 12 μm) on a polyimide substrate (polyimide thickness 12.5 μm), and removing the copper foil As a result, a polyimide substrate having a thickness of 12.5 μm was obtained.
The photosensitive layer (thickness 38 μm) of the produced photosensitive film was adhered to both surfaces of this polyimide substrate by lamination. After standing at room temperature for 10 minutes, an exposure was performed by irradiating with an ultra high pressure mercury lamp with an energy amount of 150 mJ / cm ² , the photosensitive layer was cured, and after heat treatment at 160 ° C. for 1 hour, an energy amount of 1, The photosensitive layer was cured by irradiating with 000 mJ / cm ² to increase the film strength.
A composite sample was obtained by cutting the polyimide base material on which the cured photosensitive layer obtained above was formed into a size of 20 cm × 5 cm. The obtained composite sample was wound around a cylindrical rod having a diameter of 1 cm × 20 cm, and the position of 12.5 cm from the end of the composite sample was fixed with heat-resistant tape, and then the rod was removed to obtain a length of 20 cm and a diameter of 1 cm. A flame retardant test sample was obtained.
The obtained flame retardant test sample was hung with a clamp, and a flame test was conducted by indirect flame with a 3 cm flame for 3 seconds.
〔Evaluation criteria〕
A: Meets UL94 VTM-0 B: Meets UL94 VTM-0

(Examples 2 to 23, Comparative Examples 1 to 6)
In Example 1, while maintaining the total content (solid content) of the acid-modified ethylenically unsaturated group-containing urethane resin and the acid-modified ethylenically unsaturated group-containing epoxy resin in the photosensitive composition, the type of resin, And acid-modified ethylenically unsaturated group-containing urethane resin and acid-modified ethylenically unsaturated group in the total mass (solid content total mass) of acid-modified ethylenically unsaturated group-containing urethane resin and acid-modified ethylenically unsaturated group-containing epoxy resin Except having changed the ratio of group-containing epoxy resin into the ratio of the following Tables 2-5, it carried out similarly to Example 1, and obtained each photosensitive composition, the photosensitive film, and the photosensitive laminated body.
Evaluation was performed in the same manner as in Example 1. The results are summarized in Tables 2 to 5 below.
In addition, as a comparative polyurethane resin, UXE-3024 manufactured by Nippon Kayaku Co., Ltd. was used, and as an acid-modified ethylenically unsaturated group-containing epoxy resin, ZFR-1492H ( Bisphenol F-type acid-modified ethylenically unsaturated group-containing epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), PR-300P-CP (cresol novolac-type acid-modified ethylenically unsaturated group-containing epoxy resin, manufactured by Showa Polymer Co., Ltd.), ZCR-1534 (biphenylaralkyl type acid-modified ethylenically unsaturated group-containing epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), UE-9210 (cresol novolac type acid-modified ethylenically unsaturated group-containing epoxy resin, manufactured by DIC Corporation) Solid content concentration 40% by weight) was used.

  As apparent from Tables 2 to 5, it can be seen that all the samples of the present invention are remarkably excellent in folding resistance and resolution, and that both are excellent in insulation and flame retardancy. On the other hand, none of the comparative samples has satisfactory folding resistance.

Claims (18)

It contains a binder resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. As the binder resin, at least one kind of acid-modified ethylenically unsaturated group-containing polyurethane resin and a side chain represented by the following general formula (EP) Each of the acid-modified ethylenically unsaturated group-containing epoxy resins having a partial structure is contained, and the acid-modified ethylenically unsaturated group-containing polyurethane resin is represented by the following general formula (UE1). It has a partial structure, has a mass average molecular weight of 5,000 to 60,000, an acid value of solid content of 20 mg KOH / g to 120 mg KOH / g, and an ethylenically unsaturated group equivalent of 0.5 mmol / g. The photosensitive composition characterized by being -2.0 mmol / g.

In the general formula (EP), one of R ^A1 and R ^A2 represents an unsaturated aliphatic group, and the other represents a saturated or unsaturated aliphatic group having a carboxyl group or an aromatic group having a carboxyl group. Represent. R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom or a substituent.

In the general formula (UE1), L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, and is an ethylenically unsaturated group. Represents a divalent linking group in which one group having a substituent is substituted. 2. The photosensitive composition according to claim 1, wherein the group having an ethylenically unsaturated group substituted for L ^UE has a group represented by any one of the following general formulas (1) to (3). .

In General formula (1), R < ¹ > -R < ³ > represents a hydrogen atom or monovalent organic group each independently. X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In General formula (2), R < ⁴ > -R < ⁸ > represents a hydrogen atom or monovalent organic group each independently. Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents a hydrogen atom or a monovalent organic group. The photosensitive composition according to claim 1 or 2, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a partial structure represented by the following general formula (U1).

In the general formula (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group. The photosensitive composition according to claim 3, wherein L ^U1 in the general formula (U1) has a molecular weight in terms of HO—L ^U1 —OH of 400 to 8,000. The photosensitive composition according to claim 3, wherein L ^U1 in the general formula (U1) has a molecular weight in terms of HO-L ^U1 -OH of 500 to 5,000.   The photosensitive composition according to claim 1, wherein the acid-modified ethylenically unsaturated group-containing polyurethane resin has a group having a carboxyl group at a polymer terminal. The photosensitive acid according to any one of claims 1 to 6, wherein the acid-modified ethylenically unsaturated group-containing epoxy resin is represented by any one of the following general formulas (P1) to (P3). Sex composition.

In the general formulas (P1) to (P3), R ^e1 represents a group represented by the general formula (EP) or an epoxy group. R ^e3 represents a hydrogen atom or a methyl group. R ^e3 and ^e3 each independently represent a hydrogen atom, an alkyl group or an aryl group. n ^{e1 to} n ^e3 each independently represents a number of 1 or more. However, R ^e1 is not ^{entirely an} epoxy group in the molecule. Further, a plurality of R ^e1 present in the molecule may be the same or different from each other, a plurality of R ^e3 to R ^e5 present in the molecule may be the same or different from each other. Y represents —O—, —C (═O) —O—, —O—C (═O) — or —N (Rx) —. Here, Rx represents a hydrogen atom or a substituent. La is an alkylene group or ^a divalent group having —O—, —C (═O) —O—, —O—C (═O) — or —O—C (═O) —O— in the linking chain. Represents a linking group. L ^b represents a divalent linking group having at least an alkyl partial structure, a cycloalkyl partial structure, or an aryl partial structure. L ^c and L ^d each independently represent a divalent linking group. The photosensitive composition according to claim 7, wherein the acid-modified ethylenically unsaturated group-containing epoxy resin is represented by any one of the following general formulas (P1-1) to (P3-1). .

In the general formulas (P1-1) to (P3-1), R ^e1 represents a group represented by the general formula (EP) or an epoxy group. R ^e2 and R ^e3 each independently represent a hydrogen atom or a methyl group, and R ^{e4 to} R ^e9 each independently represent a hydrogen atom, an alkyl group, or an aryl group. n ^e1 and n ^e2 each independently represent a number of 1 or more, and n ^e3 represents 0 or a number of 1 or more. However, R ^e1 is not ^{entirely an} epoxy group in the molecule. A plurality of R ^e1 present in the molecule may be the same or different, and a plurality of R ^e2 and R ^e3 present in the molecule may be the same or different. In R ^{e4 to} R ^e9 , each of the plurality of R ^{e4 to} R ^e9 present in the molecule may be the same as or different from each other.   The photosensitive composition according to claim 8, wherein the acid-modified ethylenically unsaturated group-containing epoxy resin is represented by the general formula (P3-1). One of ^{R A1} and ^{R A2} in the general formula (EP) is, -CH = CH ₂ or -C _(CH 3) = any one of claims 1-9, characterized in that the CH ₂ The photosensitive composition as described in any one of.   The ratio of the acid-modified ethylenically unsaturated group-containing urethane resin in the total solid mass of the acid-modified ethylenically unsaturated group-containing urethane resin and the acid-modified ethylenically unsaturated group-containing epoxy resin is 55% by mass. The photosensitive composition according to claim 1, wherein the content is 95% by mass or less.   Furthermore, a phosphorus series flame retardant is contained, The photosensitive composition of any one of Claims 1-11 characterized by the above-mentioned.   A photosensitive dry film comprising the photosensitive composition according to any one of claims 1 to 12 on a carrier film.   It has a photosensitive layer containing the photosensitive composition of any one of Claims 1-12 on a base material, The photosensitive laminated body characterized by the above-mentioned.   It has a photosensitive layer containing the photosensitive composition of any one of Claims 1-12 on a base material, It has a resist pattern obtained by photocuring this photosensitive layer, It is characterized by the above-mentioned. Flexible wiring board.   The flexible wiring board according to claim 15, wherein the base material is a polyimide film.   A photosensitive film according to any one of claims 1 to 12 is applied onto a carrier film and dried to obtain a photosensitive dry film, and then the photosensitive dry film is used on the substrate. A method for producing a flexible wiring board, comprising: forming a photosensitive layer on the substrate, and exposing and developing the photosensitive layer to form a resist pattern.   The permanent pattern formation method characterized by exposing with respect to the photosensitive layer containing the photosensitive composition of any one of Claims 1-12.