JP2013020094A - Photosensitive composition, photosensitive dry film, photosensitive laminate, flexible wiring board, and permanent pattern formation method - Google Patents

Abstract

Provided is a photosensitive composition having improved plating resistance without impairing folding resistance.
An acid-modified ethylenically unsaturated group-containing resin, a photopolymerization initiator, a crosslinking agent having an epoxy group, a triazine ring compound having an unsubstituted amino group, and a specific organophosphate metal salt, each containing the triazine Photosensitivity wherein the solid content in the composition of the ring compound is 1% by mass or more and 5% by mass or less, and the solid content in the composition of the metal phosphate is 10% by mass or more and 30% by mass or less. Composition.
[Selection figure] None

Description

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

  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.

  As the photosensitive composition as described above, a composition containing (A) a binder polymer, (B) an organic filler, (C) a photopolymerizable compound, and (D) a photopolymerization initiator is proposed. (Patent Document 1).

  Conventionally, the surface of the copper clad laminate has been treated with formic acid, but in recent years, sulfuric acid / hydrogen peroxide has been used to ensure the smoothness of the copper surface. As a result, it becomes more difficult to ensure the adhesion between the solder resist and copper. This is because the formic acid treatment roughens the surface and thus the anchor effect works, but the sulfuric acid / hydrogen peroxide treatment makes the surface smoother and the anchor effect cannot be expected.

Patent Document 2 describes that it is effective to contain melamine or the like in order to improve the adhesion to the base metal. However, under the circumstances as described above, a means for further improving the adhesion is demanded.
Furthermore, the solder resist material for flexible substrates is required to have folding resistance as well as such adhesion (plating resistance).

JP 2010-169810 A JP 2010-282003 A

  An object of the present invention is to achieve the following objects in order to solve the above-described problems. That is, the present invention is a photosensitive composition with improved plating resistance, even on a smooth surface without impairing the folding resistance, and further, the performance of insulation, resolution and flame retardancy as a solder resist. Maintaining a folding resistance and plating resistance, a solder resist, and a photosensitive composition that achieves both adhesion with a base metal, particularly copper, and a photosensitive dry film using the photosensitive composition, An object is to provide a photosensitive laminate, a flexible wiring board, and a method for forming a permanent pattern.

Means for solving the problems are as follows.
(1) An acid-modified ethylenically unsaturated group-containing resin, a photopolymerization initiator, a crosslinking agent having an epoxy group, a triazine ring compound having an unsubstituted amino group, and a metal phosphate represented by the following general formula (PA) The solid content in the composition of the triazine ring compound is 1% by mass or more and 5% by mass or less, and the solid content in the composition of the metal phosphate is 10% by mass or more and 30% by mass. % Of the photosensitive composition.

In the general formula (PA), ^AP and ^BP each independently represent an alkyl group or an aryl group, and M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na or K is represented. m represents an integer of 1 to 4.
(2) The photosensitive composition according to (1), wherein the triazine ring compound is represented by the following general formula (T).

In the general formula (T), R ^T1 and R ^T2 are each independently an amino group, an alkylamino group, an arylamino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Represents.
(3) The photosensitive composition according to (1), wherein the triazine ring compound is melamine, benzoguanamine or acetoguanamine.
(4) The photosensitive composition according to (1), wherein the triazine ring compound is melamine.
(5) The photosensitive composition according to any one of (1) to (4), wherein the acid-modified ethylenically unsaturated group-containing resin is an acid-modified ethylenically unsaturated group-containing polyurethane resin. object.
(6) The acid-modified ethylenically unsaturated group-containing resin is an acid-modified ethylenically unsaturated group-containing polyurethane resin having a partial structure represented by the following general formula (U1): The photosensitive composition of any one of (5).

In the general formula (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.
(7) wherein ^{L U1} in formula (U1) ^{_{is, - (CH 2 CH 2 O}} ) n U1 CH 2 CH 2 -, - _[CH 2 CH _(CH 3) O] ⁿ U1 _-CH 2 CH (CH _{3 ) -, - (CH 2 CH} 2 CH 2 CH 2 O) n U1 -CH 2 CH 2 CH 2 CH 2 -, the structure represented by the following general formula (LL1), represented by the following general formula (LL2) The photosensitive composition according to (6), which is a polybutadiene diol residue represented by a structure or the following general formula (LL3).

Here, n ^{U1 to} n ^U4 each independently represents a number of 1 or more. R ^LL1 and R ^LL2 each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group.
(8) The photosensitive composition according to (6) or (7), wherein the molecular weight of L ^U1 in the general formula (U1) is 400 to 8,000.
(9) The photosensitive composition according to (6) or (7), wherein the molecular weight of L ^U1 in the general formula (U1) is 500 to 5,000.
(10) The acid-modified ethylenically unsaturated group-containing resin is an acid-modified ethylenically unsaturated group-containing polyurethane resin having a partial structure represented by the following general formula (UE1): The photosensitive composition of any one of (9).

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 has an ethylenic side chain. A divalent linking group having one unsaturated group is represented.
(11) L ^UE in the general formula (UE1) is composed of a divalent aliphatic group, an oxygen atom, a nitrogen atom, a sulfur atom, or a combination thereof, in which the main chain bonded to the oxygen atom of two urethane bonds (10) The photosensitive composition as described above.
(12) The photosensitive composition as described in (10) or (11), wherein the general formula (UE1) is represented by the following general formula (G1).

In General Formula (G1), R ^{1 to} R ³ each independently represents a hydrogen atom or a substituent, A represents a divalent organic group, X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Represent. Here, R ¹² represents a hydrogen atom or a substituent.
(13) The acid-modified ethylenically unsaturated group-containing resin 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 ethylenically unsaturated. The photosensitive composition according to any one of (1) to (12), wherein the group equivalent is 0.05 mmol / g to 2.0 mmol / g.
(14) In the acid-modified ethylenically unsaturated group-containing polyurethane resin, the acid-modified ethylenically unsaturated group-containing polyurethane resin has a partial structure represented by the general formula (U1) as HO-L ^U1- OH. (L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group) The solid content mass ratio in terms of conversion, having 10 to 60%, (6) to (13) The photosensitive composition of any one of Claims 1.
(15) The photosensitive composition according to any one of (1) to (14), wherein the acid-modified ethylenically unsaturated group-containing resin has a group having a carboxyl group at a polymer terminal. .
(16) The acid-modified ethylenically unsaturated group-containing resin includes at least one diisocyanate compound, at least one diol compound having an ethylenically unsaturated group and two hydroxyl groups, and at least one having a carboxyl group and two hydroxyl groups. It is an acid-modified ethylenically unsaturated group-containing polyurethane resin obtained by reacting each kind of diol compound and at least one diol compound having neither ethylenically unsaturated group nor carboxyl group. (1) The photosensitive composition of any one of (15).
(17) The photosensitive composition according to (16), wherein the diisocyanate compound has a bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type or anthracene type skeleton.
(18) A photosensitive dry film comprising the photosensitive composition according to any one of (1) to (17) on a carrier film.
(19) A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of (1) to (17) on a substrate.
(20) Having a photosensitive layer containing the photosensitive composition according to any one of (1) to (17) on a substrate, and having a resist pattern obtained by photocuring the photosensitive layer A flexible wiring board characterized by comprising:
(21) The flexible wiring board according to (20), wherein the substrate is a polyimide film.
(22) A photosensitive dry film is obtained by applying and drying the photosensitive composition according to any one of (1) to (17) 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.
(23) A method for forming a permanent pattern, comprising exposing a photosensitive layer containing the photosensitive composition according to any one of (1) to (17).

  According to the present invention, a photosensitive composition having improved plating resistance, and further maintaining insulation, resolution, and flame retardancy performance as a solder resist, even on a smooth surface without impairing folding resistance. In addition, a photosensitive composition that achieves cohesion between folding resistance and plating resistance, a solder resist and a base metal, particularly copper, and a photosensitive dry film and a photosensitive composition using the photosensitive composition. A laminate, a flexible wiring board, and a permanent pattern forming method can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention includes an acid-modified ethylenically unsaturated group-containing resin (binder), a photopolymerization initiator, a crosslinking agent having an epoxy group, a triazine compound having an unsubstituted amino group, and a metal phosphate. It contains at least a salt, and further contains other components as necessary.

<Binder>
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acid-modified ethylenically unsaturated group-containing polyurethane resins, ethylenically unsaturated group-containing polycarboxylic acid resins, and acid-modified ethylenic resins. Examples thereof include an unsaturated group-containing epoxy resin, a resin containing an ethylenically unsaturated group and a carboxyl group, and a polyimide precursor. Among these, in the present invention, an acid-modified ethylenically unsaturated group-containing polyurethane resin and an acid-modified ethylenically unsaturated group-containing epoxy resin are preferable, and an acid-modified ethylenically unsaturated group-containing polyurethane resin is more preferable.
In the present invention, a vinyl group is used to mean a vinyl group that may have a substituent. These binders are described in detail below.
<< 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.
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 is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.05 mmol / g to 2.0 mmol / g. Preferably, 0.5 mmol / g to 1.9 mmol / g is more preferable, 0.75 mmol / g to 1.8 mmol / g is more preferable, and 1.1 mmol / g to 1.8 mmol / g is particularly preferable. When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 2.0 mmol / g, folding resistance may be deteriorated.
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.
There is no restriction | limiting in particular as acid-modified urethane resin which has an ethylenically unsaturated bond in a side chain, According to the objective, it can select suitably, For example, the following General formula (1)-(3) is included in the side chain. What has at least 1 among the functional groups represented by these 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.
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 the general formula (6), L ¹ represents an 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 the polyurethane resin has a partial structure represented by the following general formula (UE1). become.

In the general formulas (UE) and (UE1), L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, Represents a divalent linking group having one ethylenically unsaturated group in the chain.

  The compound represented by the general formula (UE) is preferably a compound represented by the following general formulas (UE-1) to (UE-6). In addition, the compound represented by the following general formula (UE-7) is a preferable compound other than the compound represented by the said general formula (UE).

In General Formulas (UE-1) to (UE-7), 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-7), the compounds represented by the general formulas (UE-1) to (UE-6) are preferable, and the general formula (UE- The compound represented by 6) is more 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.

  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 CH 2 O) n U1 -CH 2 CH 2 CH 2 CH 2 -, represented by the following general formula (LL1) A structure, a structure represented by the following general formula (LL2), or a polybutadienediol residue represented by the following general formula (LL3).

Here, R ^LL1 and R ^LL2 each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group. n ^{U1 to} n ^U4 each independently represents a number of 1 or more.
As the divalent chain hydrocarbon group, an alkylene group, an alkenylene group or an alkynylene group is preferable. These may have a branched or substituted group. More preferable carbon number is 2-8, ethylene group, trimethylene group, propylene group, tetramethylene group, 2-methyl-tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, 2-butenylene group, A 2-butynylene group is a suitable example.
The divalent cyclic hydrocarbon group is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. . A single ring or a condensed ring may be used, and a single ring is preferable. Either an aromatic ring or an aliphatic ring may be used. Among these, preferred examples of the aromatic ring include a benzene ring and a naphthalene ring, and preferred examples of the aliphatic ring include a cyclohexane ring and a bicyclo [2.2.2] octane ring.
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-5).

  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 is preferably 400 to 8,000, more preferably 500 to 5,000, still more preferably 600 to 3,000, and 800 to 2 Is particularly preferred. 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 may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 2.0 mmol / g, 0.5 mmol / g to 1.90 mmol / g is more preferable, 0.75 mmol / g to 1.80 mmol / g is more preferable, and 1.1 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. Depending on the purpose, as the diol component, 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 may be added 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. And at least one selected from the following general formulas (III-1) to (III-5) or the aforementioned general formula (LL3) according to the purpose: A reaction product of at least one selected from polymer diols in the range of 000, in the obtained reaction product and the molecules represented by the following general formulas (IV-1) to (IV-16) It may be obtained by reacting an epoxy group with a compound having an ethylenically unsaturated group.

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 group or carbon having 2 to 10 carbon atoms. Several to 10 arylene groups are more preferable. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is More preferred. 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 group having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or a carbon number of 1 An alkyl group having 6 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms are more preferable. 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.

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. m represents an integer of 2 to 4.
In the general formulas (III-1) to (III-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represents an integer of 2 or more, and 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-5) or the aforementioned general formula (LL3), and 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. The component is selected from polymer diols having a mass average molecular weight of 800 to 3,000, represented by general formulas (III-1) to (III-5) or the aforementioned general formula (LL3), depending on the purpose. And a reaction product of at least one selected from the group consisting of general formulas (III-1) to (III-5) or the aforementioned general formula (LL3) with a low molecular weight diol having a weight average molecular weight of 500 or less and not containing a carboxyl group Further, a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any one of the general formulas (IV-1) to (IV-16) is reacted with An alkali-soluble photocrosslinkable polyurethane resin having an acid value of 20 mgKOH / g to 120 mgKOH / g, obtained accordingly.

  In the polyurethane resin (ii), the above-mentioned polyurethane is used instead of or in combination with the compounds represented by the general formulas (III-1) to (III-5) or the general formula (LL3). It is preferable to use the diol compound represented by the general formula (U) described in the resin (i), and the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin. The mass ratio is the same as in the case of the polyurethane resin (i) described above.

  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, it is finally treated with alcohols or amines. Synthesized with no isocyanate groups remaining.

<< Content of acid-modified ethylenically unsaturated group-containing polyurethane resin (i), (ii) >>
The acid-modified ethylenically unsaturated group-containing polyurethane resin (i) or (ii) used in the present invention can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. is there. For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.
There is no restriction | limiting in particular as content in the said photosensitive composition of the polyurethane resin (i) and (ii) used by this invention, Although it can select suitably according to the objective, 5 mass%-80 mass% Is preferable, 20 mass%-75 mass% is more preferable, and 30 mass%-70 mass% is especially preferable.
When the content is less than 5% by mass, the folding resistance may not be kept good. When the content exceeds 80% by mass, the heat resistance may be broken. When the content is within the particularly preferable range, it is advantageous in terms of achieving both good folding resistance and heat resistance.

<Metallic phosphates>
The metal phosphate is a metal phosphate represented by the following general formula (PA).

In General Formula (PA), each of ^AP and ^BP independently represents any of a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, and an aryl group. Represent. M represents any of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K. m represents an integer of 1 to 4.
As said ^AP and ^BP , a linear C1-C6 alkyl group is preferable, a methyl group, an ethyl group, and n-propyl group are more preferable, and an ethyl group is especially preferable. As said M, Al is preferable. Moreover, as said m, 3 is preferable.
Examples of the metal phosphate represented by the general formula (PA) include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, Zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate and any mixtures thereof And those selected from the group consisting of: Commercially available products can be used, such as Exolite OP-935, Exolite OP-930, Exolite OP1230, Exolite OP-1240, Exolite OP-1312 (all manufactured by Clariant Japan Co., Ltd.), which are aluminum phosphinates. It is done.

  The average particle diameter of the metal phosphate represented by the general formula (PA) is preferably 5.0 μm or less, and more preferably 4 μm or less. Moreover, it is also preferable to refine | purify a commercial item and to make it contain in a photosensitive composition as 1.0 micrometer or less, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is further more preferable. When the average particle diameter exceeds 5.0 μm, folding resistance may be lowered and folding resistance may be insufficient. There is no restriction | limiting in particular as a lower limit of the said average particle diameter, Although it can select suitably according to the objective, 0.001 micrometer or more is preferable and 0.01 micrometer or more is further more preferable.

The maximum particle diameter of the metal phosphate represented by the general formula (PA) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm or less, more preferably 5 μm or less, and 3 μm. The following are particularly preferred: There is no restriction | limiting in particular as a lower limit of the said maximum particle diameter, Although it can select suitably according to the objective, 1 micrometer or more is preferable.
The average particle size and the maximum particle size can be measured using, for example, a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). Specifically, the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method.
The average particle size is defined as a particle size having an integrated value of 50% when expressed as an integrated (cumulative) weight percentage, and is defined as d50 (D50) or the like.
The maximum particle size is defined as a particle size having an integrated value of 100% and is defined as d100 (D100) or the like.

  The method for setting the metal phosphate represented by the general formula (PA) to the average particle size and the maximum particle size is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a method using a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor.

  As content in the said photosensitive composition solid content of the phosphoric acid metal salt represented by the said general formula (PA), they are 10 mass parts or more and 30 mass parts or less, and 10 mass parts-20 mass parts are preferable. When the content is less than 10 parts by mass, flame retardancy may be insufficient, and when it exceeds 30 parts by mass, folding resistance may be deteriorated.

<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 Of these 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.

<Crosslinking agent having epoxy group>
Examples of the crosslinking agent having an epoxy group include an epoxy compound (for example, at least two oxirane groups in one molecule within a range that does not adversely affect developability and the like in order to improve film strength after curing of the photosensitive layer. Epoxy compounds having an oxirane group as described in JP 2007-47729 A, and the like.

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

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said crosslinking agent which has the said epoxy group, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, 3 The mass% to 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.

<Triazine ring compound having unsubstituted amino group>
The photosensitive composition of the present invention contains a triazine ring compound having an unsubstituted amino group.
The triazine ring compound is preferably represented by the following general formula (T).

In the general formula (T), R ^T1 and R ^T2 are each independently an amino group or an alkylamino group (preferably having 1 to 18 carbon atoms such as methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, 2-ethylhexylamino, n-octylamino, cyclopropylamino, diallylamino), arylamino group (preferably having 6 to 18 carbon atoms, such as phenylamino, N-methyl-N-phenylamino, naphthylamino), alkyl group (Preferably having 1 to 18 carbon atoms, for example, methyl, ethyl, isopropyl, n-butyl, t-butyl, 2-ethylhexyl, n-octyl, dodecyl, hexadecyl), aryl group (preferably having 6 to 18 carbon atoms) , For example, phenyl, naphthyl), a heterocyclic group (preferably a 3-7 membered ring, More preferably, it is a 5- or 6-membered ring, and the hetero atom is a nitrogen atom, oxygen atom or sulfur atom. Examples of the hetero ring include a pyrrolidine ring, piperazine ring, piperidine ring, morpholine ring, furan ring, thiophene ring, Pyridine ring), an alkoxy group (preferably having 1 to 18 carbon atoms, methoxy, ethoxy, 2-ethylhexyloxy, n-octyloxy, dodecyloxy), an aryloxy group (preferably having 6 to 18 carbon atoms such as phenoxy, Naphthoxy), alkylthio group (preferably having 1 to 18 carbon atoms, such as methylthio, ethylthio, n-butylthio, 2-ethylhexylthio, n-octylthio) or arylthio group (preferably having 6 to 18 carbon atoms, such as phenylthio, naphthylthio) ).
One of R ^T1 and R ^T2 is preferably an amino group. The remaining one is preferably an amino group, an alkyl group or an aryl group.
Examples of the compound represented by the general formula (T) include the following compounds.

The compound represented by the general formula (T) is more preferably melamine, benzoguanamine, or acetoguanamine, and particularly preferably melamine.
As content in the said photosensitive composition solid content of the said triazine ring compound, they are 1 mass% or more and 5 mass% or less, and 1.5 mass%-4 mass% are preferable. When the content is 1% by mass or more, the plating resistance is improved, and when the content is 5% by mass or less, the folding resistance is not adversely affected.
In the present invention, in addition to the triazine ring compound, for example, a curing accelerator described in paragraph [0093] of JP-A-2008-250074 may be used in combination.

<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, Polyfunctional acrylates and methacrylates such as tricyclodecane dimethanol (meth) acrylate and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid are more preferable.
As the polymerizable compound, polyfunctional acrylates and methacrylates such as those having two or more acryloyloxy groups and methacryloyloxy groups, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid are particularly 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.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include fillers, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and further groups. Adhesion promoters and other auxiliaries to the material surface (for example, conductive particles, fillers, antifoaming agents, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) May be used in combination.
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.
However, in the present invention, it is preferable not to contain inorganic fine particles which are inorganic fillers in the photosensitive composition. Even if it is contained, the solid content ratio of the photosensitive composition is less than 10% by mass, more preferably 1% by mass. Is less than.
Examples of the thermal polymerization inhibitor include paragraphs [0101] to [0102] of JP-A-2008-250074.
Examples of the plasticizer include paragraphs [0103] to [0104] of JP-A-2008-250074.
Examples of the colorant include paragraphs [0105] to [0106] of JP-A-2008-250074.
Examples of the adhesion promoter include paragraphs [0107] to [0109] of JP-A-2008-250074.

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

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.
There is no restriction | limiting in particular as said support body, According to the objective, it can select suitably, For example, the support body of 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 dry 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 base material is a substrate to be processed on which a photosensitive layer is formed, or a material to be transferred onto which at least the photosensitive layer of the photosensitive dry 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 film of the present invention is performed. For example, a method of transferring and laminating can be used.

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 material, performing at least any one of a heating and pressurization. In addition, when the said photosensitive 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 material.
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)
The printed circuit board of the present invention, particularly the flexible wiring board preferred in the present invention, comprises at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further appropriately selected as necessary. It has the member of.
There is no restriction | limiting in particular as another member, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned.

  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, mass average molecular weight, and ethylenically unsaturated group equivalent 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 a sample solution, 62 columns of TSKgelGMH were used, 200 μL of sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. did. Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
<Equivalent ethylenically unsaturated group>
The ethylenically unsaturated group equivalent was determined by measuring the bromine number according to JIS K2605.

酸変性のエチレン性不飽和基含有エポキシ樹脂Ｄ
ＺＡＲ−２０３６Ｈ（日本化薬社製） The following acid-modified ethylenically unsaturated group-containing resins A to D were prepared as follows.

Acid-modified ethylenically unsaturated group-containing epoxy resin D
ZAR-2036H (Nippon Kayaku Co., Ltd.)

(Preparation Example 1)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin A>
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 A solution having a solid content concentration of 40% by mass. The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin A 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)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin B>
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 synthesized. The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin B 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 mmol / g.

(Preparation Example 3)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin C>
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) malic acid were combined with 14.45 g (0.098 mol) 2,2-bis (hydroxymethyl) butyric acid (DMBA). Instead of a combination of 44.45 g (0.278 mol) of glycerol monomethacrylate (GLM) and 6.03 g (0.045 mol) of malic acid, 23.46 g (0.094) of 4,4-diphenylmethane diisocyanate (MDI) Mol), 47.30 g of hexamethylene diisocyanate (HMDI) (0. 81 mol) is replaced with a combination of 75.08 g (0.300 mol) of 4,4-diphenylmethane diisocyanate (MDI) and 12.61 g (0.075 mol) of hexamethylene diisocyanate (HMDI), In the same manner as in Preparation Example 1, an acid-modified ethylenically unsaturated group-containing polyurethane resin (PU8) solution having a solid content concentration of 40% by mass was synthesized. The resulting acid-modified ethylenically unsaturated group-containing polyurethane resin C had a mass average molecular weight of 8,000, a solid content acid value of 69 mgKOH / g, and an ethylenically unsaturated group equivalent of 1.82 mmol / g. .

(Preparation Example 4)
<Preparation of acid-modified ethylenically unsaturated group-containing epoxy resin D>
ZAR-2036H (trade name; acid-modified ethylenically unsaturated group-containing epoxy resin manufactured by Nippon Kayaku Co., Ltd.) was diluted with cyclohexanone to adjust the solid content concentration to 40% by mass, and acid-modified ethylenically unsaturated group-containing epoxy Used as Resin D.

Example 1
-Composition of photosensitive composition solution-
-Solution of the ethylenically unsaturated group-containing polyurethane resin A of Preparation Example 1 (adjusted to a solid content of 40% by mass) ... 114.3 parts by mass-Exolit OP-935 (manufactured by Clariant Japan) ... 15 parts by mass Coloring pigment: HELIOGEN BLUE D7086 (manufactured by BASF) ... 0.07 parts by massColoring pigment: Riotol Yellow D0960 (manufactured by BASF) ... 0.02 parts by massPolymerizable compound: Lipoxy VR-60 ( 18.7 parts by mass / initiator: IRG907 (manufactured by Ciba Specialty Chemicals) ... 2.0 parts by mass / sensitizer: DETX-S (manufactured by Nippon Kayaku Co., Ltd.) ... 0.02 parts by mass-Reaction aid: EAB-F (Hodogaya Chemical Co., Ltd.) ... 0.07 parts by mass-Melamine (Wako Pure Chemical Industries, Ltd.) -1.8 parts by mass-Thermal cross-linking agent: Epototo YDF-170 (manufactured by Nippon Steel Chemical Co., Ltd.) ... 20 parts by mass-Coating aid: Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc. 3 mass% methyl ethyl ketone solution) ... 0.23 parts by mass / cyclohexanone (solvent) ... 33.78 parts by mass

-Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through-holes, copper thickness 18 μm) to an acid cleaning 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.
About the obtained photosensitive laminated body, the resist pattern was formed with the evaluation method shown below.

-Exposure process-
A predetermined pattern can be obtained from the polyethylene terephthalate film (support) side with respect to the photosensitive layer in the prepared photosensitive laminate using a blue-violet laser exposure pattern having a predetermined pattern by an ultrahigh pressure mercury lamp. In this way, an energy amount of 200 mJ / cm ² was irradiated and exposed 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 permanent pattern is subjected to heat treatment at 160 ° C. for 1 hour, and then the surface of the permanent pattern is cured by irradiating with an energy amount of 1,000 mJ / cm ² to increase the film strength. A test plate was prepared.

It used for the following evaluation. The results are shown in Table 1.
<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 copper foil line pattern of / 100 μm was created.

The polyimide layer with the copper foil line pattern thus obtained was laminated with the photosensitive layer of the prepared photosensitive film on the copper foil line pattern side, and allowed to stand at room temperature for 10 minutes, and then with an ultrahigh pressure mercury lamp, the energy amount was 150 mJ / cm. ² is exposed to light, the photosensitive layer is cured, and after heat treatment at 160 ° C. for 1 hour, the photosensitive layer is cured by irradiating with an energy amount of 1,000 mJ / cm ² to form a film. A laminate for evaluation was obtained by increasing the strength.
The obtained laminate for evaluation was cut into 5 mm × 10 cm square, bent 180 ° in the long side direction with the line pattern side outside, put a predetermined weight on the bent part for 3 seconds, and evaluated folding resistance according to the following criteria did.
〔Evaluation criteria〕
○: No crack at 200 g. Δ: No crack at 10 g and no more than 10% of the length of the bent side. Nox: No more than 10% of the bent side at 200 g.

<Evaluation of plating resistance>
The surface of a substrate for flexible printed wiring boards (manufactured 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) was subjected to an acid cleaning treatment. Except for using one, INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm) was used on the surface of the photosensitive layer of the photosensitive laminate produced in the same manner as the photosensitive laminate. After forming an independent fine line pattern of 30 μm to 1,000 μm with an optimal amount of light energy and allowing to stand at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a copper-clad laminate (flexible print) 2% to 3 times the shortest development time with a 1 mass% sodium carbonate aqueous solution at 30 ° C. at a spray pressure of 0.15 MPa on the entire surface of the photosensitive layer on the wiring substrate). Time (or 40 seconds to 60 seconds) and spray development, to dissolve away the uncured regions. Then, after heat-processing (post-baking) at 160 degreeC for 1 hour, the whole surface exposure was further performed with the ultrahigh pressure mercury lamp at 1,000 mJ / cm < ² >, and the soldering resist pattern (permanent pattern) was formed.

The cured resin pattern (permanent pattern) was subjected to an acid degreasing solution (Sulcup ACL-
007, manufactured by Uemura Kogyo Co., Ltd.) for 5 minutes and then washed with water. Next, an activator solution (KAT-450, Uemura at 22 ° C. for 90 seconds in a soft etch solution at 22 ° C. (sodium peroxodisulfate 125 g / L, sulfuric acid 18 g / L), 120 seconds in a 10% sulfuric acid aqueous solution at 22 ° C. (Manufactured by Kogyo Co., Ltd.) for 120 seconds and immersed in a 10% aqueous sulfuric acid solution at 22 ° C. for 60 seconds. In addition, it washed with water between each process so far. Thereafter, electroless Ni plating (Nimden NDF-2, manufactured by Uemura Kogyo Co., Ltd.) is performed at 85 ° C. for 35 minutes. After washing with water, a gold plating solution at 75 ° C. (Okuno Pharmaceutical Co., Ltd., OPC Mudengor, pH 12) -13, thick gold plating 0.3 μm) for 4 minutes, after electroless gold plating, after 3 minutes immersion in running water and water washing, further immersed in warm water at 60 ° C. for 3 minutes After sufficiently washing with water, it was dried and an electroless gold-plated test substrate was obtained.
A peel test was performed on the cured resin pattern (permanent pattern) after the plating test with reference to JIS K5600-5-6, and evaluation was performed according to the following criteria.
○: No abnormality after peel test ×: Peeling observed during peel test

(Examples 2-5, Comparative Examples 1-7)
In Example 1, the photosensitive composition, the photosensitive film, etc. were obtained like Example 1 except having replaced the resin, the compound which has a triazine ring, and the flame retardant with the thing of Table 1.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

  The curing accelerator used above is the following compound.

Phosphorus-containing compound used Metal phosphate salt OP-935 (trade name; manufactured by Clariant Japan)
Condensed phosphate ester CR-741 (trade name; manufactured by Daihachi Chemical Co., Ltd.)

In Examples 1 to 5, both folding resistance and plating resistance were sufficient.
On the other hand, Comparative Examples 1 to 7 had a problem in either folding resistance or plating resistance.

Claims (23)

It contains an acid-modified ethylenically unsaturated group-containing resin, a photopolymerization initiator, a crosslinking agent having an epoxy group, a triazine ring compound having an unsubstituted amino group, and a metal phosphate represented by the following general formula (PA). The solid content in the composition of the triazine ring compound is 1% by mass or more and 5% by mass or less, and the solid content in the composition of the metal phosphate is 10% by mass or more and 30% by mass or less. There is a photosensitive composition.

In the general formula (PA), ^AP and ^BP each independently represent an alkyl group or an aryl group, and M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na or K is represented. m represents an integer of 1 to 4. The photosensitive composition according to claim 1, wherein the triazine ring compound is represented by the following general formula (T).

In the general formula (T), R ^T1 and R ^T2 are each independently an amino group, an alkylamino group, an arylamino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Represents.   The photosensitive composition according to claim 1, wherein the triazine ring compound is melamine, benzoguanamine or acetoguanamine.   The photosensitive composition according to claim 1, wherein the triazine ring compound is melamine.   The photosensitive composition according to any one of claims 1 to 4, wherein the acid-modified ethylenically unsaturated group-containing resin is an acid-modified ethylenically unsaturated group-containing polyurethane resin. The acid-modified ethylenically unsaturated group-containing resin is an acid-modified ethylenically unsaturated group-containing polyurethane resin having a partial structure represented by the following general formula (U1). The photosensitive composition of Claim 1.

In the general formula (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group. ^{L U1} in the general formula (U1) ^{_{is, - (CH 2 CH 2 O}} ) n U1 CH 2 CH 2 -, - _[CH 2 CH _(CH 3) O] _{^{n U1 -CH 2 CH (CH 3}} ) -, _{- (CH 2 CH 2 CH 2} CH 2 O) n U1 -CH 2 CH 2 CH 2 CH 2 -, the structure or the following the structure represented by the following general formula (LL1), represented by the following general formula (LL2) The photosensitive composition according to claim 6, which is a polybutadiene diol residue represented by the general formula (LL3).

Here, n ^{U1 to} n ^U4 each independently represents a number of 1 or more. R ^LL1 and R ^LL2 each independently represent a divalent chain hydrocarbon group or a divalent cyclic hydrocarbon group. The photosensitive composition according to claim 6 or 7, wherein the molecular weight of L ^U1 in the general formula (U1) is 400 to 8,000. The photosensitive composition according to claim 6 or 7, wherein the molecular weight of L ^U1 in the general formula (U1) is 500 to 5,000. The acid-modified ethylenically unsaturated group-containing resin is an acid-modified ethylenically unsaturated group-containing polyurethane resin having a partial structure represented by the following general formula (UE1). The photosensitive composition of Claim 1.

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 has an ethylenic side chain. A divalent linking group having one unsaturated group is represented. L ^UE in the general formula (UE1) is characterized in that the main chain bonded to the oxygen atoms of two urethane bonds is composed of a divalent aliphatic group, an oxygen atom, a nitrogen atom, a sulfur atom, or a combination thereof. The photosensitive composition according to claim 10. The photosensitive composition according to claim 10 or 11, wherein the general formula (UE1) is represented by the following general formula (G1).

In General Formula (G1), R ^{1 to} R ³ each independently represents a hydrogen atom or a substituent, A represents a divalent organic group, X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Represent. Here, R ¹² represents a hydrogen atom or a substituent.   The acid-modified ethylenically unsaturated group-containing resin 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. It is 0.05 mmol / g-2.0 mmol / g, The photosensitive composition of any one of Claims 1-12 characterized by the above-mentioned. In the acid-modified ethylenically unsaturated group-containing polyurethane resin, the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is changed to HO-L ^U1 -OH (L ^U1 Represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group), and has a solid content mass ratio in terms of 10 to 60% according to any one of claims 6 to 13 The photosensitive composition as described.   The photosensitive composition according to any one of claims 1 to 14, wherein the acid-modified ethylenically unsaturated group-containing resin has a group having a carboxyl group at a polymer terminal.   The acid-modified ethylenically unsaturated group-containing resin is at least one diisocyanate compound, at least one diol compound having an ethylenically unsaturated group and two hydroxyl groups, and at least one diol having a carboxyl group and two hydroxyl groups. 2. An acid-modified ethylenically unsaturated group-containing polyurethane resin obtained by reacting a compound and at least one diol compound having neither an ethylenically unsaturated group nor a carboxyl group, respectively. The photosensitive composition of any one of -15.   The photosensitive composition according to claim 16, wherein the diisocyanate compound has a bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type or anthracene type skeleton.   A photosensitive dry film comprising the photosensitive composition according to any one of claims 1 to 17 on a carrier film.   It has a photosensitive layer containing the photosensitive composition of any one of Claims 1-17 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 1-17 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 20, wherein the substrate is a polyimide film.   The photosensitive composition according to any one of claims 1 to 17 is applied on 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 1-17.