Photosensitive resin composition, cured product thereof, and multilayer material

Abstract

The present invention provides a composition containing a maleimide compound composed of maleic anhydride and a diamine derived from a dimer acid, which has good developability and further has high insulating reliability and flexibility, and a cured product containing the composition. [Solution] The resin composition comprises a maleimide compound (I) which is a reaction product of diamine (a-1) derived from dimer acid and maleic anhydride, and a reactive polycarboxylic acid resin (II) which is a reaction product of a reactive epoxy carboxylate resin which is a reaction product of epoxy resin (b-1) and compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and a polybasic acid anhydride (b-3).

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product thereof, and uses thereof. More specifically, the present invention relates to a photosensitive resin composition that exhibits excellent developability and whose cured product exhibits excellent dielectric properties, flexibility, and high insulation reliability, and uses thereof.

Background Art

[0002] Since photosensitive resin compositions can be microfabricated based on the principle of photolithography, they are applied to various resist materials, printed wiring boards, and the like. In recent years, with the miniaturization, high density, and high communication speed of information and communication devices, in addition to low dielectric properties, properties related to long-term reliability such as substrate adhesion, low water absorption, and moisture resistance, and from the perspective of environmental measures, negative photosensitive materials that can be developed with a weak alkaline aqueous solution have been demanded.

[0003] As a material that satisfies the above properties to some extent, a carboxylate resin obtained by reacting a general epoxy resin with (meth)acrylic acid and a carboxylic acid compound having a hydroxyl group is known, and it is also known that this resin has resist ink suitability (Patent Document 1). However, since the carboxylate resin has an ester group with a high polarity (dipole moment) and a secondary hydroxyl group remaining unreacted with the carboxylic acid compound, which have an adverse effect on dielectric properties, low water absorption, and moisture resistance, it is required to achieve both of the above physical properties at a higher level.

[0004] In addition, as another photosensitive resin, a bismaleimide compound obtained by reacting a diamine derived from dimer acid described in Patent Document 2 with a tetracarboxylic dianhydride having an alicyclic skeleton and maleic anhydride has been studied. It is characterized by having excellent dielectric properties, low water absorption, moisture resistance, and high substrate adhesion due to improved flexibility by the long-chain alkyl group derived from dimer acid. However, a maleimide compound composed of a diamine derived from dimer acid and maleic anhydride can obtain a cured film with high insulation reliability and flexibility due to the long-chain alkyl group derived from dimer acid. However, due to the high hydrophobicity of the long-chain alkyl group derived from dimer acid, development with an alkaline aqueous solution was difficult.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, an object of the present invention is to improve the above-mentioned conventional problems, provide a composition containing a maleimide compound composed of a diamine derived from dimer acid and maleic anhydride having good developability, and further having high insulation reliability and flexibility, and a cured product containing the same.

Means for Solving the Problems

[0007] As a result of earnest research to achieve the above object, the present inventors have found that a resin composition containing, simultaneously, a diamine (a-1) derived from dimer acid, a maleimide compound (I) composed of maleic anhydride, an epoxy resin (b-1), a reactive epoxy carboxylate resin which is a reaction product of the epoxy resin (b-1) and a compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and a reactive polycarboxylic acid resin (II) which is a reaction product of the reactive epoxy carboxylate resin and a polybasic acid anhydride (b-3) is developable in a weakly alkaline aqueous solution, and its cured film has high insulation reliability and flexibility. It has been found that it has flexibility.

[0008] That is, the present invention relates to the following (1) to (8). (1) A resin composition containing a diamine (a-1) derived from dimer acid, a maleimide compound (I) which is a reaction product of maleic anhydride, an epoxy resin (b-1), a reactive epoxy carboxylate resin which is a reaction product of the epoxy resin (b-1) and a compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and a reactive polycarboxylic acid resin (II) which is a reaction product of the reactive epoxy carboxylate resin and a polybasic acid anhydride (b-3). (2) The resin composition according to (1), wherein the maleimide compound (I) is composed of a diamine (a-1) derived from dimer acid, a polybasic acid anhydride (a-2), and maleic anhydride. (3) The resin composition according to (2), wherein the polybasic acid anhydride (a-2) has an alicyclic structure. (4) The maleimide compound (I) is represented by the following general formula (1):

[0009] [Chemical formula] [In formula (1), R 1 represents a divalent hydrocarbon group (a) derived from dimer acid, R 2 represents a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from dimer acid, R 3 represents any one selected from the group consisting of a divalent hydrocarbon group (a) derived from dimer acid and a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from dimer acid, and R 4and R 5 is at least one organic group selected from a tetravalent organic group having 6 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a crosslinked structure, and a tetravalent organic group having 4 to 40 carbon atoms and having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. R 4 and R 5 is contained in an amount of 5 to 95 mol% when the total amount of and R 1 and R 4 is 100 mol%. m is an integer from 1 to 30, n is an integer from 0 to 30, and when m is 2 or more, a plurality of R 2 and R 5 may be the same or different from each other, and when n is 2 or more, a plurality of R The resin composition according to any one of (1) to (3), represented by (5) The epoxy resin (b-1) is represented by the following general formula (2):

[0010]

Chemical formula

Advantages of the Invention

[0011] The resin composition containing a diamine (a-1) derived from a dimer acid, a maleimide compound (I) which is a reaction product of maleic anhydride, an epoxy resin (b-1), and a reactive epoxy carboxylate resin which is a reaction product of a compound (b-2) having a polymerizable ethylenic unsaturated group and a carboxy group in one molecule and a polybasic acid anhydride (b-3), a reactive polycarboxylic acid resin (II), not only gives a cured product having high insulation reliability and flexibility, but also has good developability. Therefore, the product of the present invention can be suitably used for a film-forming material which requires development using a weak alkali and has high insulation reliability.

[0012] Preferably, for example, it can be used for applications such as solder resist for printed wiring boards, protective films for multilayer printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resist for flexible printed wiring boards, plating resist, photosensitive optical waveguides, etc., which particularly require high insulation reliability.

Embodiments for Carrying Out the Invention

[0013] The present invention is obtained by including a diamine (a-1) derived from a dimer acid, a maleimide compound (I) which is a reaction product of maleic anhydride, an epoxy resin (b-1), a reactive epoxy carboxylate resin which is a reaction product of a compound (b-2) having a polymerizable ethylenic unsaturated group and a carboxy group in one molecule, and a reactive polycarboxylic acid resin (II) which is a reaction product of a polybasic acid anhydride (b-3), and the features of the present invention are exhibited.

[0014] Hereinafter, the present invention will be described in detail according to its preferred embodiments.

[0015] <Maleimide Compound (I)> The maleimide compound (I) according to the present invention has a divalent hydrocarbon group (a) derived from a dimer acid and a cyclic imide bond. Such a maleimide compound (I) can be obtained by reacting a diamine (a-1) derived from a dimer acid with maleic anhydride.

[0016] The divalent hydrocarbon group (a) derived from the dimer acid refers to a divalent residue obtained by removing two carboxyl groups from the dicarboxylic acid contained in the dimer acid. In the present invention, such a divalent hydrocarbon group (a) derived from the dimer acid can be introduced into the maleimide compound by reacting a diamine (a-1) derived from the dimer acid with a polybasic acid anhydride (a-2) and maleic anhydride, which will be described later, to form an imide bond.

[0017] In the present invention, the dimer acid is obtained by dimerizing the unsaturated bonds of unsaturated carboxylic acids such as linoleic acid, oleic acid, and linolenic acid, and then subjecting it to distillation purification. It mainly contains a dicarboxylic acid having 36 carbon atoms, and usually contains up to about 5% by mass of a tricarboxylic acid having 54 carbon atoms and up to about 5% by mass of a monocarboxylic acid, respectively. The diamine (a-1) derived from the dimer acid according to the present invention is a diamine obtained by substituting two carboxyl groups of each dicarboxylic acid contained in the dimer acid with amino groups, and is usually a mixture. In the present invention, examples of such a diamine (a-1) derived from the dimer acid include diamines such as [3,4-bis(1-aminoheptyl)6-hexyl-5-(1-octenyl)]cyclohexane, and those containing diamines in which the unsaturated bonds are saturated by further hydrogenating these diamines.

[0018] The divalent hydrocarbon group (a) derived from the dimer acid according to the present invention, which is introduced into the maleimide compound using the diamine (a-1) derived from such a dimer acid, is preferably a residue obtained by removing two amino groups from the diamine (a-1) derived from the dimer acid. Further, when obtaining the maleimide compound according to the present invention using the diamine (a-1) derived from the dimer acid, one kind of the diamine (a-1) derived from the dimer acid may be used alone, or two or more kinds having different compositions may be used in combination. Furthermore, as the diamine (a-1) derived from such a dimer acid, commercially available products such as "PRIAMINE 1074" (manufactured by Croda Japan Co., Ltd.) may be used.

[0019] In the present invention, the cyclic imide bond refers to a bond in which two imide bonds are cyclically linked. In the present invention, such a cyclic imide bond can be introduced into the maleimide compound by reacting a polybasic acid anhydride (a-2) with a divalent organic group (b) other than the above-mentioned diamine (a-1) derived from the dimer acid and the divalent hydrocarbon group (a) derived from the dimer acid described later to form an imide bond.

[0020] In the present invention, the maleimide compound (I) is preferably represented by the following general formula (1). In general formula (1), R 4 and R 5 are structures derived from the polybasic acid anhydride (a-2).

[0021]

Chemical formula

[0022] In formula (1), R 1 represents a divalent hydrocarbon group (a) derived from the dimer acid, R 2 represents a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid, and R 3 represents any one selected from the group consisting of a divalent hydrocarbon group (a) derived from the dimer acid and a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid.4 and R 5 is each independently a tetravalent organic group having 6 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a crosslinked structure, and a tetravalent organic group having 4 to 40 carbon atoms and having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring, and one or more organic groups selected from these are represented by R 4 and R 5 is contained in an amount of 5 to 95 mol% when the total amount of and R is 100 mol%. m is an integer from 1 to 30, n is an integer from 0 to 30, and when m is 2 or more, there are a plurality of R 1 and R 4 may be the same or different from each other, and when n is 2 or more, there are a plurality of R 2 and R 5 may be the same or different from each other.

[0023] In the present invention, the polybasic acid anhydride (a-2) is preferably the polybasic acid anhydride (a-2) represented by the following general formula (3). The polybasic acid anhydride (a-2) represented by the following general formula (3) has an alicyclic structure adjacent to the anhydride group.

[0024]

Chemical formula

[0025] (In the formula, Cy is a tetravalent hydrocarbon ring group having 4 to 40 carbon atoms, and the hydrocarbon ring group may contain an aromatic ring.)

[0026] In the present invention, the polybasic acid anhydride (a-2) preferably contains a structure represented by the following general formulas (3-1) to (3-16). The polybasic acid anhydride (a-2) represented by formulas (3-1) to (3-16) has a structure containing a tetravalent organic group having 4 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a crosslinked structure, and a tetravalent organic group having 4 to 40 carbon atoms and having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring.

[0027]

Chem.

[0028] (In general formula (3-4), X1 is an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent cross-linked structure formed by linking two or more of them. In general formulas (3-6), (3-15), and (3-16), X2 is a divalent cross-linked structure formed by linking two or more organic groups selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a divalent organic group having 1 to 3 carbon atoms, or an arylene group.)

[0029] As the polybasic acid anhydride (a-2) containing a tetravalent organic group having a monocyclic or condensed polycyclic alicyclic structure and having 4 to 40 carbon atoms, a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a crosslinked structure linked to each other, and a tetravalent organic group having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring, specifically, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,4,5-bicyclohexanetetracarboxylic dianhydride (H-BPDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic dianhydride and other alicyclic tetracarboxylic dianhydrides or compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione and other semi-alicyclic tetracarboxylic dianhydrides or compounds in which hydrogen atoms of these aromatic rings are substituted with an alkyl group or a halogen atom can be mentioned.In addition, aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, etc., and aromatic acid dianhydrides such as bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or compounds in which the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms, and acid dianhydrides having amide groups can be mentioned. These can be used in combination with two or more acid dianhydrides containing an alicyclic structure or a semi-alicyclic structure having 4 to 40 carbon atoms.

[0030] Furthermore, from the viewpoints of high exposure sensitivity, high resolution, and insulation reliability of the cured film, those not containing an aromatic ring are preferred. The reason is that those containing an aromatic ring tend to have a reduced photosensitivity due to a deteriorated hue. Among the polybasic acid anhydrides not containing an aromatic ring, when 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) is used, it is preferably highly photocurable.

[0031] Furthermore, as the maleimide compound (I) according to the present invention, it may be a maleimide compound obtained by reacting the diamine (a-1) derived from the dimer acid, a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid, the tetracarboxylic dianhydride, and the maleic anhydride. By copolymerizing the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid, it becomes possible to control the required physical properties as needed, such as further reducing the tensile elastic modulus of the resulting cured product.

[0032] The divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid (hereinafter sometimes simply referred to as organic diamine (b)) refers to, in the present invention, a diamine other than the diamines contained in the diamine (a-1) derived from the dimer acid. Such divalent organic groups (b) other than the divalent hydrocarbon group (a) derived from the dimer acid are not particularly limited, and examples thereof include aliphatic diamines such as 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane; aromatic diamines such as 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(aminomethyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, and 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenyl sulfone; 3,3'-diaminodiphenyl sulfone; 4,4-diaminobenzophenone; 4,4-diaminodiphenyl sulfide; and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Among these, from the viewpoint of obtaining a cured product having a lower tensile elastic modulus, aliphatic diamines having 6 to 12 carbon atoms such as 1,6-hexamethylenediamine; diaminocyclohexanes such as 1,4-diaminocyclohexane; and aromatic diamines having an aliphatic structure having 1 to 4 carbon atoms in the aromatic skeleton such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane are more preferable. Further, when obtaining the maleimide compound (I) according to the present invention using these divalent organic groups (b) other than the divalent hydrocarbon group (a) derived from the dimer acid, one of these divalent organic groups (b) other than the divalent hydrocarbon group (a) derived from the dimer acid may be used alone or in combination of two or more.

[0033] The divalent hydrocarbon group (a) derived from the dimer acid in the formula (1) is as described above. In the present invention, the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid in the formula (1) refers to a divalent residue obtained by removing two amino groups from the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid. However, in the same compound, the divalent hydrocarbon group (a) derived from the dimer acid and the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid are not the same. Further, the tetravalent organic group in the formula (1) refers to a tetravalent residue obtained by removing two groups represented by -CO-O-CO- from the tetracarboxylic dianhydride.

[0034] In the formula (1), m is the number of repeating units containing the divalent hydrocarbon group (a) derived from the dimer acid (hereinafter, sometimes referred to as a dimer acid-derived structure), and represents an integer of 1 to 30. When the value of m exceeds the upper limit, the solubility in a solvent decreases, and particularly the solubility in a developing solution during development described later decreases. Further, from the viewpoint that the solubility in a developing solution during development becomes suitable, the value of m is particularly preferably 3 to 10.

[0035] In the formula (1), n is the number of repeating units containing the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid (hereinafter, sometimes referred to as an organic diamine-derived structure), and represents an integer of 0 to 30. When the value of n exceeds the upper limit, the flexibility of the obtained cured product deteriorates, and the resin becomes hard and brittle. Further, from the viewpoint that a cured product having a low elastic modulus can be obtained, the value of n is particularly preferably 0 to 10.

[0036] Furthermore, when m in the formula (1) is 2 or more, R 1 and R 4 may be the same or different from each other. When n in the formula (1) is 2 or more, R 2 and R 5They may be the same or different from each other. Further, as the maleimide compound represented by the formula (1), the dimer acid-derived structure and the organic diamine-derived structure may be random or block.

[0037] In addition, when obtaining the maleimide compound (I) according to the present invention from the diamine (a-1) derived from the dimer acid, the maleic anhydride, the polybasic anhydride (a-2), and, if necessary, the organic diamine (b), when the reaction rate is 100%, the n and m can be represented by the mixed molar ratio of all the diamines contained in the diamine (a-1) derived from the dimer acid, the organic diamine (b), the maleic anhydride, and the polybasic anhydride (a-2). That is, (m + n):(m + n + 2) is represented by (the total number of moles of all the diamines contained in the diamine (a-1) derived from the dimer acid and the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid):(the total number of moles of the maleic anhydride and the polybasic anhydride (a-2)), m:n is represented by (the number of moles of all the diamines contained in the diamine (a-1) derived from the dimer acid):(the number of moles of the divalent organic group (b) other than the divalent hydrocarbon group (a) derived from the dimer acid), and 2:(m + n) is represented by (the number of moles of the maleic anhydride):(the number of moles of the polybasic anhydride (a-2)).

[0038] The maleimide compound (I) in the present invention includes those obtained by directly maleimidizing the diamine derived from the dimer acid without using the polybasic anhydride (a-2).

[0039] As the maleimide compound (I) according to the present invention, commercially available compounds may be appropriately used. For example, "BMI-689", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-2500", "BMI-2560", "BMI-3000" (manufactured by DESIGNER MOLECURES Inc.) can be preferably used. Further, as the maleimide compound (I) according to the present invention, one kind may be used alone or two or more kinds may be used in combination.

[0040] The maleimide compound (I) in the present invention is preferably 10% by mass to 95% by mass based on all components. As the content of the maleimide compound (I) increases, the insulation reliability and flexibility tend to increase, but it has an adverse effect on the alkali developability. Therefore, a more preferable range is 30% by mass to 70% by mass.

[0041] <Reactive polycarboxylic acid resin (II)> The reactive polycarboxylic acid resin (II) in the present invention can be obtained by reacting a reactive epoxy carboxylate resin, which is a reaction product of an epoxy resin (b-1) and a compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, with a polybasic acid anhydride (b-3).

[0042] In the present invention, the epoxy resin (b-1) is the following general formula (2):

[0043] [Chemical formula] [In formula (2), R 6 represents an aromatic ring or a hydrocarbon group containing an alicyclic skeleton having 1 to 40 carbon atoms, and R 7 may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 40 carbon atoms. Also, x is an integer from 1 to 30.] Examples include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, epoxy compounds containing a naphthyl skeleton, epoxy compounds containing a fluorenyl skeleton, and the like.

[0044] Examples of novolak epoxy resins include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade names), DEN-431, DEN-439 (above, manufactured by The Dow Chemical Company, trade names), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, manufactured by Nippon Kayaku Co., Ltd., trade names), EPN-1138, EPN-1235, EPN-1299 (above, manufactured by BASF Japan Ltd., trade names), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (above, manufactured by DIC Corporation, trade names), etc., which are commercially available. Examples of bisphenol A type epoxy resins or bisphenol F type epoxy resins include Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, manufactured by Mitsubishi Chemical Corporation, trade names), DER-330, DER-301, DER-361 (above, manufactured by The Dow Chemical Company, trade names), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade names), etc., which are commercially available. Examples of biphenyl type epoxy resins include NC3000, NC3000H, NC3000L, NC3100 (above, manufactured by Nippon Kayaku Co., Ltd.), GK3207 (manufactured by Tohto Kasei Co., Ltd.), YX4000HK (manufactured by Japan Epoxy Resins Co., Ltd.), BPAE (manufactured by Nippon Steel Chemical Co., Ltd.), etc., which are commercially available. Examples of dicyclopentadiene type epoxy resins include HP7200, HP7200H, HP7200HH (above, manufactured by DIC Corporation), XD-1000, XD-1000-L, XD-10002L (above, manufactured by Nippon Kayaku Co., Ltd.), etc., which are commercially available. Examples of epoxy compounds containing a naphthyl skeleton include HP4032, 4700, 4770, 5000, 6000 (manufactured by DIC Corporation), NC-7000, 7300 (manufactured by Nippon Kayaku Co., Ltd.), ESN-175 (manufactured by Nippon Steel Chemical Co., Ltd.), ESN-475V (manufactured by Tohto Kasei Co., Ltd.), etc., which are commercially available.Examples of epoxy compounds containing a fluorenyl skeleton include OGSOL PG-100, OGSOL EG-200 (both manufactured by Osaka Gas Chemical Co., Ltd.), etc., which are commercially available. In particular, dicyclopentadiene-type epoxy resins are more preferred because of their high compatibility with the maleimide compound (I) and improved alkali developability.

[0045] In the present invention, the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule is reacted to impart reactivity to active energy rays. There is no limitation as long as there is at least one ethylenically unsaturated group and at least one carboxy group in the molecule.

[0046] In the present invention, examples of the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or reaction products of saturated or unsaturated dibasic acids and unsaturated group-containing monoglycidyl compounds. Examples of the (meth)acrylic acids include monocarboxylic acid compounds containing one carboxy group in one molecule, such as (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, half esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides and (meth)acrylate derivatives having one hydroxyl group in one molecule, and half esters which are equimolar reaction products of saturated or unsaturated dibasic acids and monoglycidyl (meth)acrylate derivatives; and polycarboxylic acid compounds having a plurality of carboxy groups in one molecule, such as half esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides and (meth)acrylate derivatives having a plurality of hydroxyl groups in one molecule, and half esters which are equimolar reaction products of saturated or unsaturated dibasic acids and glycidyl (meth)acrylate derivatives having a plurality of epoxy groups.

[0047] Among these, as the epoxy resin (b-1) and the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, it is preferably a monocarboxylic acid. Even when a monocarboxylic acid and a polycarboxylic acid are used in combination, the value represented by the molar amount of the monocarboxylic acid / the molar amount of the polycarboxylic acid is preferably 15 or more. Most preferably, from the viewpoint of sensitivity to active energy rays when used as a resin composition, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid can be mentioned. As the compound having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in one molecule, those having no hydroxyl group in the compound are preferred.

[0048] The compound (c-1) having both a hydroxyl group and a carboxy group in one molecule, which is optionally used in the present invention (hereinafter, also simply referred to as "compound (c-1)"), is reacted for the purpose of introducing a hydroxyl group into a carboxylate compound. These include a compound having one hydroxyl group and one carboxy group in one molecule, a compound having two or more hydroxyl groups and one carboxy group in one molecule, and a compound having one or more hydroxyl groups and two or more carboxy groups in one molecule. Examples of the compound having one hydroxyl group and one carboxy group in one molecule include hydroxypropionic acid, hydroxybutyric acid, hydroxystearic acid, etc. Examples of the compound having two or more hydroxyl groups and one carboxy group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutyric acid, etc. Examples of the compound having one or more hydroxyl groups and two or more carboxy groups in one molecule include hydroxyphthalic acid, etc. Among these, those having two or more hydroxyl groups in one molecule are preferred in consideration of the effects of the present invention. Further, from the viewpoint of the stability of the carboxylation reaction, those having one carboxy group in one molecule are preferred. Most preferably, those having two hydroxyl groups and one carboxy group in one molecule are preferred. Considering the availability of raw materials, dimethylolpropionic acid and dimethylolbutyric acid are particularly suitable. As the compound having one or more hydroxyl groups and one or more carboxyl groups in one molecule, those having no polymerizable ethylenically unsaturated group in the compound are preferred.

[0049] The charging ratio of the epoxy resin (b-1), the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and the compound (c-1) used as required in this carboxylation reaction should be appropriately changed according to the application. That is, when all epoxy groups are carboxylated, since no unreacted epoxy groups remain, the storage stability as a reactive epoxy carboxylate resin is high. In this case, only the reactivity due to the introduced double bond will be utilized.

[0050] By reducing the charging amounts of the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule and the compound (c-1) and leaving unreacted residual epoxy groups, it is also possible to utilize the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy groups, such as the polymerization reaction by a photo cationic catalyst or a thermal polymerization reaction, in a complex manner. However, in this case, attention should be paid to the storage of the reactive epoxy carboxylate resin and the consideration of the manufacturing conditions.

[0051] When producing a reactive epoxy carboxylate resin without leaving epoxy groups, the total of the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule and the compound (c-1) used as required is preferably 90 to 120 equivalent% with respect to 1 equivalent of the epoxy resin (b-1). If it is within this range, production under relatively stable conditions is possible. When the charging amount of the carboxylic acid compound is larger than this, it is not preferable because excess compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule and the compound (c-1) will remain.

[0052] Also, when leaving epoxy groups remaining, it is preferable that the total of the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule and the compound (c-1) used as necessary is 20 to 90 equivalent % with respect to 1 equivalent of the epoxy resin (b-1). If it deviates from this range, the effect of composite curing becomes weak. Of course, in this case, sufficient attention is required regarding gelation during the reaction and the stability over time of the reactive epoxy carboxylate resin.

[0053] The carboxylation reaction can be carried out without a solvent or by diluting with a solvent and reacting. The solvent that can be used here is not particularly limited as long as it is an inert solvent with respect to the carboxylation reaction.

[0054] The preferable amount of the solvent used should be appropriately adjusted according to the viscosity and use of the resulting resin, but it is preferably used so as to be 90 to 30 mass % of the solid content, more preferably 80 to 50 mass %.

[0055] Examples of the solvent used in the carboxylation reaction include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, decane, and petroleum ether, white gasoline, solvent naphtha, etc., which are mixtures thereof, ester solvents, ether solvents, ketone solvents, and the like.

[0056] Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butylene glycol monomethyl ether acetate; and polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate.

[0057] Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; and cyclic ethers such as tetrahydrofuran.

[0058] Examples of ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0059] In addition, it can be carried out in a single or mixed organic solvent such as the reactive compound (D) (hereinafter also simply referred to as "reactive compound (D)") described later. In this case, it is preferable because it can be directly used as a composition when used as a curable resin composition.

[0060] In the carboxylation reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the reactants, that is, the epoxy resin (b-1) and the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, the compound (c-1) used as necessary, and optionally a solvent and others. The reaction temperature at that time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate and the like.

[0061] Also, a thermal polymerization inhibitor can be used. As the thermal polymerization inhibitor, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene and the like.

[0062] The carboxylation reaction is terminated at the point when the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while sampling appropriately.

[0063] Next, the reactive polycarboxylic acid resin (II) used in the present invention will be described. These reactive polycarboxylic acid resins are obtained by reacting the reactive epoxy carboxylate resin with a polybasic acid anhydride (b-3). The reason for introducing a carboxyl group by this acid addition step is, for example, to impart solubility in alkaline water to the non-irradiated portion of active energy rays in applications where resist patterning etc. are required, and to impart adhesion to metals, inorganic substances and the like. This acid addition step involves reacting the polybasic acid anhydride (b-3) with the hydroxyl group of the epoxy carboxylate compound to introduce a carboxyl group via an ester bond.

[0064] As the polybasic acid anhydride (b-3), for example, any compound having a cyclic acid anhydride structure in one molecule can be used, but succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hydrogenated trimellitic anhydride, trimellitic anhydride or maleic anhydride, which are excellent in alkali aqueous solution developability, heat resistance, hydrolysis resistance, etc., are preferable.

[0065] The reaction for adding the polybasic acid anhydride (b-3) can be carried out by adding the polybasic acid anhydride (b-3) to the solution of the epoxy carboxylate compound. The addition amount may be appropriately changed according to the use.

[0066] It is preferable to charge a calculated amount such that the solid content acid value (conforming to JIS K5601-2-1:1999) of the reactive polycarboxylic acid resin (II) obtained by the reaction of the reactive epoxy carboxylate resin and the polybasic acid anhydride (b-3) is 20 to 120 mg·KOH / g, more preferably 60 to 120 mg·KOH / g. When the solid content acid value is within this range, the alkali aqueous solution developability in the resin composition of the present invention exhibits good performance. That is, it has good patterning properties and a wide control range against overdevelopment, and no excessive acid anhydride remains.

[0067] During the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is 0.1 to 10 parts by mass based on the total amount of the reactants, namely the epoxy resin (b-1), the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, the reactive epoxy carboxylate compound obtained from the compound (c-1), the polybasic acid anhydride (b-3), and optionally a solvent and other substances. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate, and the like.

[0068] This acid addition reaction can be carried out without a solvent or by diluting with a solvent. The solvent is not particularly limited as long as it does not affect the acid addition reaction. Also, when a solvent is used in the previous step of the epoxy carboxylation reaction, it can be directly subjected to the acid addition reaction without removing the solvent on the condition that it does not affect the acid addition reaction. The solvent that can be used may be the same as those that can be used in the carboxylation reaction.

[0069] The preferred amount of the solvent used should be appropriately adjusted according to the viscosity and use of the resulting resin, but it is preferably used so that the solid content is 90 to 30% by mass, more preferably 80 to 50% by mass.

[0070] In addition, it can be carried out in a single or mixed organic solvent such as the reactive compound (D). In this case, when used as a curable resin composition, it is preferable because it can be directly used as a composition.

[0071] Also, it is preferable to use a thermal polymerization inhibitor, and examples of the thermal polymerization inhibitor include the same ones as those in the epoxy carboxylation reaction.

[0072] This acid addition reaction is terminated when the acid value of the reactant reaches within the range of plus or minus 10% of the set acid value while appropriately sampling. The preferable molecular weight range of the resulting reactive polycarboxylic acid resin (II) is such that the polystyrene-reduced weight average molecular weight in GPC (gel permeation chromatography) measurement is in the range of 500 to 50,000, more preferably 800 to 30,000, and particularly preferably 800 to 10,000. When the molecular weight is smaller than this, the toughness of the cured product is not fully exhibited, and when it is too large, the viscosity becomes high and coating, development, etc. become difficult.

[0073] In the present invention, the reactive polycarboxylic acid resin (II) is preferably 90% by mass to 5% by mass based on all components. As the content of the reactive polycarboxylic acid resin (II) increases, the alkali development time becomes shorter, but on the other hand, the dielectric properties and flexibility decrease. Also, as the content of the reactive polycarboxylic acid resin (II) decreases, the dielectric properties and electrical insulation properties improve, but the alkali development time becomes longer. Therefore, a more preferable range of the content of the reactive polycarboxylic acid resin (II) is 70% by mass to 30% by mass based on all components.

[0074] The reactive polycarboxylic acid resin (II) of the present invention may contain a reactive compound (D) other than the reactive polycarboxylic acid resin (II). Specific examples of the reactive compound (D) that can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, cation reaction type other epoxy compounds, and vinyl compounds sensitive to both.

[0075] Examples of the acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, etc.

[0076] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.

[0077] Examples of polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of hydroxybivalic acid neopentyl glycol, poly(meth)acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethanolpropane tri(meth)acrylate, and its ethylene oxide adduct, pentaerythritol tri(meth)acrylate, and its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate, and its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate, and its ethylene oxide adduct, etc.

[0078] Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like. Examples of styrenes include styrene, methyl styrene, ethyl styrene, and the like. Examples of other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, and the like.

[0079] Furthermore, examples of so-called reactive oligomers include urethane acrylate having a functional group sensitive to active energy rays and a urethane bond in the same molecule, polyester acrylate having a functional group sensitive to active energy rays and an ester bond in the same molecule, epoxy acrylate derived from other epoxy resins and having a functional group sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination, and the like.

[0080] In addition, the cationic reactive monomer is not particularly limited as long as it is a compound having an epoxy group in general. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (such as "Silacure UVR-6110" manufactured by Union Carbide Corporation), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide Corporation), limonene dioxide (such as "Celloxide 3000" manufactured by Daicel Corporation), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxide, bis(3,4-epoxycyclohexyl)adipate (such as "Silacure UVR-6128" manufactured by Union Carbide Corporation), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, and the like can be mentioned.

[0081] Among these, as the reactive compound (D), acrylates which are radical curable are most preferable. In the case of the cationic type, since the carboxylic acid reacts with the epoxy group, depending on the type of the reactive compound (D), a two-component mixed system may be used.

[0082] The reactive compound (D) in the present invention is from 0% by mass to 95% by mass, more preferably from 3% by mass to 80% by mass, based on all the components. Examples of the other components include a photopolymerization initiator, other additives, a coloring material, a curing accelerator, and a volatile solvent added for viscosity adjustment for the purpose of imparting coating applicability and the like. Other components that can be used are exemplified below.

[0083] The resin composition of the present invention may further contain a coloring pigment, which is used to color the resin composition of the present invention as a coloring material. It is presumed that the hydroxyl groups of the reactive polycarboxylic acid resin (II) used in the resin composition of the present invention exhibit particularly excellent affinity for pigments, that is, dispersibility. As a result of good dispersibility, the pigment concentration can be increased. Also, in a composition that requires development, better dispersibility is more suitable, good patterning properties are exhibited, and there are also fewer development residues in the developed and dissolved part, which is suitable. That is, the reactive polycarboxylic acid resin (II) used in the resin composition of the present invention has a high affinity with coloring pigments such as carbon black, and can exhibit good developability even at a high pigment concentration, and can also be suitably used for color resists, resist materials for color filters, particularly black matrix materials, black column spacers, etc.

[0084] Examples of the coloring pigment include organic pigments such as phthalocyanine-based, azo-based, and quinacridone-based pigments, and inorganic pigments such as carbon black and titanium oxide. Among these, carbon black is preferred because of its high dispersibility.

[0085] The resin composition of the present invention can further contain a photopolymerization initiator. As the photopolymerization initiator, a radical-type photopolymerization initiator, a cationic photopolymerization initiator, or a photo-base initiator is preferred. Examples of radical photoinitiators include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2 - diethoxy - 2 - phenylacetophenone, 1,1 - dichloroacetophenone, 2 - hydroxy - 2 - methyl - phenylpropan - 1 - one, diethoxyacetophenone, 1 - hydroxycyclohexyl phenyl ketone, and 2 - methyl - 1 - [4 - (methylthio)phenyl] - 2 - morpholino - propan - 1 - one; anthraquinones such as 2 - ethylanthraquinone, 2 - t - butylanthraquinone, 2 - chloroanthraquinone, and 2 - amylanthraquinone; thioxanthones such as 2,4 - diethylthioxanthone, 2 - isopropylthioxanthone, and 2 - chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4 - benzoyl - 4'-methyldiphenyl sulfide, and 4,4'-bis(methylamino)benzophenone; phosphine oxides such as 2,4,6 - trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6 - trimethylbenzoyl)phenylphosphine oxide; and other known general radical photoinitiators.

[0086] Examples of cationic photoinitiators include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine - based initiators, borate - based initiators, and other photoacid generators.

[0087] Examples of photo - base initiators include photo - base initiators such as TRD - 001 (manufactured by Nippon Kayaku Co., Ltd.), TRD - 008 (manufactured by Nippon Kayaku Co., Ltd.), WPBG - 300 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPBG - 345 (manufactured by Fujifilm Wako Pure Chemical Corporation), PBG - 266 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPBG - 018 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPBG - 027 (manufactured by Fujifilm Wako Pure Chemical Corporation), WPBG - 140 (manufactured by Fujifilm Wako Pure Chemical Corporation), and WPBG - 165 (manufactured by Fujifilm Wako Pure Chemical Corporation).

[0088] Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate, N,N-diethylaminophenyldiazonium hexafluorophosphate (such as Sun-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.), and the like. Examples of iodonium salts of Lewis acids include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and the like. Examples of sulfonium salts of Lewis acids include triphenylsulfonium hexafluorophosphate (such as Cyracure UVI-6990 manufactured by Union Carbide Corporation), triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide Corporation), and the like. Examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate, and the like.

[0089] Examples of other halides include 2,2,2-trichloro-[1-4'-(dimethyl ethyl)phenyl]ethanone (such as Trigonal PI manufactured by AKZO), 2,2-dichloro-1-4-(phenoxyphenyl)ethanone (such as Sandray 1000 manufactured by Sandoz), α,α,α-tribromomethyl phenyl sulfone (such as BMPS manufactured by Seitetsu Kagaku Co., Ltd.), and the like. Examples of triazine-based initiators include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (such as Triazine A manufactured by Panchim), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl-(piperonyl)-6-triazine (such as Triazine PP manufactured by Panchim), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (such as Triazine B manufactured by Panchim), 2[2'(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd., etc.), 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0090] Examples of borate-based photoinitiators include NK-3876 and NK-3881 manufactured by Nippon Senshoku Dye Co., Ltd. Examples of other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-bisimidazole (bisimidazole manufactured by Koganei Chemical Co., Ltd., etc.), 2,2-azobis(2-amino-propane) dihydrochloride (V50, etc. manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (VA044, etc. manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), [eta-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,eta)-(methylethyl)-benzene] iron(II) hexafluorophosphate (Irgacure261, etc. manufactured by Ciba Geigy), bis(eta5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyr-1-yl)phenyl] titanium (CGI-784, etc. manufactured by Ciba Geigy), and the like.

[0091] In addition, azo-based initiators such as azobisisobutyronitrile and peroxide-based radical initiators sensitive to heat such as benzoyl peroxide may also be used in combination. Further, both radical-based and cationic-based photoinitiators may be used in combination. The photoinitiator can be used alone or in combination of two or more.

[0092] Among these, in consideration of the characteristics of the reactive polycarboxylic acid resin (II) of the present invention, radical-type photoinitiators are particularly preferred.

[0093] Furthermore, the resin composition of the present invention can contain a coloring pigment. As the coloring pigment, for example, those not intended for coloring, so-called extender pigments can also be used. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, and the like can be mentioned.

[0094] Furthermore, the resin composition of the present invention can contain other additives as needed. Examples of other additives include heat-curing catalysts such as melamine, thixotropy-imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and defoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants, etc.

[0095] In addition to these, as resins that do not show reactivity to active energy rays (so-called inert polymers), for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone-formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40 parts by mass in the resin composition.

[0096] In particular, when attempting to use the reactive polycarboxylic acid resin (II) for solder resist applications, it is preferable to use a generally known epoxy resin as the resin that does not show reactivity to active energy rays. This is because carboxyl groups derived from the reactive polycarboxylic acid resin (II) remain even after reaction and curing by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolysis resistance. Therefore, by using an epoxy resin, the remaining carboxyl groups are further carboxylated to form a stronger crosslinked structure. The generally known epoxy resin can use the cationic reaction type monomer.

[0097] Also, depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent can be added to the resin composition in the range of up to 50 parts by mass, more preferably up to 35 parts by mass.

[0098] The resin composition of the present invention can be easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible light rays, infrared rays, X-rays, gamma rays, laser light rays, and particle rays such as alpha rays, beta rays, and electron beams. Considering the preferred applications of the present invention, among these, ultraviolet rays, laser light rays, visible light rays, or electron beams are preferred.

[0099] In the present invention, the molding material refers to a material that is used for the purpose of putting an uncured composition into a mold, or pressing the mold, forming an object, and then causing a curing reaction by active energy rays to form the object, or irradiating the uncured composition with a focused light such as a laser to cause a curing reaction and form the object.

[0100] Specific applications include a sheet formed in a planar shape, a sealing material for protecting elements, a so-called nanoimprint material that performs fine molding by pressing a finely processed "mold" against an uncured composition, and further, peripheral sealing materials for light-emitting diodes, photoelectric conversion elements, etc., which have particularly strict thermal requirements, are listed as preferred applications.

[0101] In the present invention, the film-forming material is used for the purpose of coating the surface of a substrate. Specific applications include ink materials such as gravure ink, flexo ink, silk screen ink, offset ink, etc., coating materials such as hard coat, top coat, overprint varnish, clear coat, etc., adhesive materials such as laminating adhesives, optical disk adhesives, and various other adhesives, resist materials such as solder resist, etching resist, resist for micromachines, etc. Further, a so-called dry film, which is obtained by temporarily coating a film-forming material on a peelable substrate, forming a film, and then laminating it on the original target substrate to form a film, also falls under the category of film-forming materials.

[0102] The present invention also includes a cured product obtained by irradiating the above-mentioned curable resin composition with active energy rays, and also includes a multilayer material having a layer of the cured product.

[0103] Among these, due to the introduction of carboxyl groups in the reactive polycarboxylic acid resin (II), the adhesion to the substrate is enhanced, so it is preferably used for coating plastic substrates or metal substrates.

[0104] Furthermore, taking advantage of the characteristic that the unreacted reactive polycarboxylic acid resin (II) becomes soluble in an alkaline aqueous solution, it is also preferably used as an alkali-developable resist material composition.

[0105] In the present invention, the resist material composition refers to an active energy ray-sensitive composition that forms a film layer of the composition on a substrate and then partially irradiates it with active energy rays such as ultraviolet rays, and attempts to draw using the physical property differences between the irradiated part and the non-irradiated part. Specifically, it is a composition used for the purpose of removing the irradiated part or the non-irradiated part by dissolving it in some way, such as with a solvent or an alkaline solution, etc., to perform drawing.

[0106] The resin composition, which is the resist material composition of the present invention, can be applied to various materials capable of patterning. For example, it is particularly useful for solder resist materials and interlayer insulating materials for build-up processes. Furthermore, it is also used for electrical, electronic, and optical substrates such as printed wiring boards, optoelectronic substrates, and optical substrates as optical waveguides.

[0107] As a particularly suitable application, taking advantage of the characteristics of good heat resistance and developability, it can be used in a wide range of applications that require resin compositions, such as photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, etc. Among them, since it can exhibit good developability even at a high pigment concentration, it can also be suitably used for color resists, resist materials for color filters, especially black matrix materials, etc. It can also be suitably used for matrix materials, etc.

[0108] Furthermore, it can also be suitably used for resin compositions for insulating layers of multilayer printed wiring boards (multilayer printed wiring boards having cured products of photosensitive resin compositions as insulating layers), resin compositions for interlayer insulating layers (multilayer printed wiring boards having cured products of photosensitive resin compositions as interlayer insulating layers), resin compositions for plating formation (multilayer printed wiring boards having plating formed on cured products of photosensitive resin compositions), and the like.

[0109] Patterning using the resin composition of the present invention can be carried out, for example, as follows. The curable resin composition of the present invention is applied on a substrate by a method such as screen printing method, spray method, roll coating method, electrostatic coating method, curtain coating method, spin coating method, etc. with a film thickness of 0.1 to 200 μm, and the coating film is usually dried at a temperature of 50 to 110°C, preferably 60 to 100°C, whereby a coating film can be formed. Thereafter, high-energy rays such as ultraviolet rays are irradiated directly or indirectly on the coating film through a photomask having an exposure pattern, usually with a strength of about 10 to 2000 mJ / cm 2 and a desired pattern can be obtained using a developing solution described later, for example, by spraying, vibrating immersion, paddle, brushing, etc.

[0110] As the alkaline aqueous solution used for the above development, inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, etc. and organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, etc. can be used. Organic solvents, buffers, complexing agents, dyes or pigments can be further added to this aqueous solution.

[0111] In addition, it is particularly preferably used for dry film applications where mechanical strength before the curing reaction by active energy rays is required. That is, since the balance between the hydroxyl groups and carboxyl groups of the reactive polycarboxylic acid resin (II) used in the present invention is within a specific range, the reactive polycarboxylic acid resin (II) of the present invention can exhibit good developability.

[0112] There is no particular limitation on the method for forming the film, and various coating methods such as gravure printing methods such as gravure, relief printing methods such as flexo, stencil printing methods such as silk screen, planographic printing methods such as offset, roll coater, knife coater, die coater, curtain coater, spin coater, etc. can be arbitrarily adopted.

Examples

[0113] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples. In the examples, % indicates mass % unless otherwise specified.

[0114] The softening point, epoxy equivalent, and acid value were measured under the following conditions. 1) Epoxy equivalent: Measured by a method according to JIS K7236:2001. 2) Acid value: Measured by a method according to JIS K0070:1992. 3) The measurement conditions for GPC are as follows. Model: TOSOH HLC-8320GPC Column: Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40 °C Detector: RI (differential refractometer) Molecular weight standard: Polystyrene

[0115] <Maleimide resin (I)> [Synthesis Example 1 (I-1)] Into a 500 ml round-bottom flask equipped with a fluororesin-coated stirring bar, 110 g of toluene and 36 g of N-methylpyrrolidone were charged. Next, 85.6 g (0.16 mol) of PRIAMINE 1074 (manufactured by Croda Japan Co., Ltd.) as diamine (a-1) derived from dimer acid was added, and then 15.4 g (0.16 mol) of methanesulfonic anhydride was slowly added to form a salt. The mixture was stirred and mixed for approximately 10 minutes, and then 1,2,4,5-cyclohexanetetracarboxylic dianhydride (24.5 g, 0.08 mol) as polybasic acid anhydride (a-2) was slowly added to the stirred mixture. A Dean-Stark trap and a condenser were attached to the flask. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. The theoretical amount of water of formation from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 18.8 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water of formation. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. Next, the diluted organic layer was washed with water (100 ml × 3) to remove salts and unreacted starting materials. Thereafter, the solvent was removed under vacuum to obtain 108 g (yield 90%, Mw = 3,600) of an amber wax-like maleimide compound.

[0116] [Synthesis Example 2 (I-2)] Into a 500 ml round-bottom flask equipped with a fluororesin-coated stirring bar, 110 g of toluene and 36 g of N-methylpyrrolidone were charged. Next, 85.3 g (0.16 mol) of PRIAMINE 1074 (manufactured by Croda Japan Co., Ltd.) as diamine (a-1) derived from dimer acid was added, and then 15.4 g (0.16 mol) of methanesulfonic anhydride was slowly added to form a salt. The mixture was stirred and mixed for approximately 10 minutes, and then 4,4'-oxydiphthalic dianhydride (24.8 g, 0.08 mol) as polybasic acid anhydride (a-2) was slowly added to the stirred mixture. A Dean-Stark trap and a condenser were attached to the flask. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. The theoretical amount of water generated from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 18.8 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water generated. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. Next, the diluted organic layer was washed with water (100 ml × 3) to remove salts and unreacted starting materials. Thereafter, the solvent was removed under vacuum to obtain 106 g of a brown wax-like maleimide compound (yield 88%, Mw = 3,700).

[0117] [Synthesis Example 3 (I-3)] 110 g of toluene and 36 g of N-methylpyrrolidone were charged into a 500 ml round-bottom flask equipped with a fluororesin-coated stirring bar. Next, 460.8 g (0.85 mol) of PRIAMINE 1074 (manufactured by Croda Japan Co., Ltd.), a diamine (a-1) derived from dimer acid, was added, and then 81.7 g (0.85 mol) of methanesulfonic anhydride was slowly added as a catalyst to form a salt. The mixture was stirred and mixed for approximately 10 minutes, and 200.0 g (2.04 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water of formation. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. Next, the diluted organic layer was washed with water (100 ml × 3) to remove salts and unreacted starting materials. Thereafter, the solvent was removed under vacuum to obtain 520.0 g (yield 89%, Mw = 689) of a brown wax-like maleimide compound.

[0118] [Synthesis Example A (I-4)] 110 g of toluene and 36 g of N-methylpyrrolidone were charged into a 500 ml round-bottom flask equipped with a Teflon (registered trademark)-coated stirring bar. Next, 73.5 g (0.14 mol) of PRIAMINE 1074 (manufactured by Croda Japan Co., Ltd.) and 8.4 g (0.06 mol) of 1,3-bis(aminomethyl)cyclohexane were added, and then 18.9 g (0.20 mol) of methanesulfonic anhydride was slowly added to form a salt. The mixture was stirred and mixed for approximately 10 minutes, and then 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride (26.0 g, 0.10 mol) was slowly added to the stirred mixture. A Dean-Stark trap and a condenser were attached to the flask. The mixture was heated to reflux for 6 hours to form an amine-terminated diimide. The theoretical amount of water of formation from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 23.1 g (0.24 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours to obtain the expected amount of water of formation. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. Next, the diluted organic layer was washed with water (100 ml × 3) to remove salts and unreacted starting materials. Thereafter, the solvent was removed under vacuum to obtain 108 g (yield 90%, Mw = 2,800) of an amber wax-like maleimide compound.

[0119] <Reactive polycarboxylic acid resin (II)> [Synthesis Example 4 (II-1)] Into a 1 L four-necked flask, 330 g of XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 70 °C, epoxy equivalent 252 g / eq.) as the epoxy resin (b-1), 95 g of acrylic acid (AA) as the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, 3 g of BHT (dibutylhydroxytoluene) as a polymerization inhibitor, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by mass, and the mixture was reacted at 100 °C for 24 hours. The reaction was terminated when the solid content acid value (AV: mgKOH / g) became 3 or less, and a reactive epoxy carboxylate resin solution was obtained. The solid content acid value (mgKOH / g) was measured as a solution and converted to a value on a solid content basis. Subsequently, 180 g of THPA (1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) as the polybasic acid anhydride (b-3) and propylene glycol monomethyl ether monoacetate as a solvent were added to the obtained reactive epoxy carboxylate resin solution so that the solid content was 65%, and after heating to 100 °C, an acid addition reaction was carried out to obtain a reactive polycarboxylic acid resin (II-1) solution. The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid resin (II-1) was 110.

[0120] [Synthesis Example 5 (II-2)] Into a 1 L four-necked flask, 315 g of NC-6000 (manufactured by Nippon Kayaku Co., Ltd., softening point 60 °C, epoxy equivalent 207 g / eq.) as the epoxy resin (b-1), 110 g of acrylic acid (AA) as the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, 3 g of BHT (dibutylhydroxytoluene) as a polymerization inhibitor, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 80% by mass, and the mixture was reacted at 100 °C for 24 hours. The reaction was terminated when the solid content acid value (AV: mgKOH / g) became 3 or less, and a reactive epoxy carboxylate resin solution was obtained. The solid content acid value (mgKOH / g) was measured as a solution and converted to a value on a solid content basis. Subsequently, 158 g of THPA (1,2,3,6 - tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) as a polybasic acid anhydride (b - 3) and propylene glycol monomethyl ether monoacetate as a solvent were added to the obtained reactive epoxy carboxylate resin solution so that the solid content ratio became 65%. After heating to 100°C, an acid addition reaction was carried out to obtain a reactive polycarboxylic acid resin (II - 2) solution. The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid resin (II - 2) was 100.

[0121] [Synthesis Example 6 (II - 3)] In a 1 L four - necked flask, 312 g of NC - 3500 (manufactured by Nippon Kayaku Co., Ltd., softening point 70°C, epoxy equivalent 205 g / eq.) as an epoxy resin (b - 1), 111 g of acrylic acid (AA) as a compound (b - 2) having both a polymerizable ethylenic unsaturated group and a carboxyl group in one molecule, 3 g of BHT (dibutylhydroxytoluene) as a polymerization inhibitor, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content ratio became 80 mass%. The reaction was carried out at 100°C for 24 hours, and the reaction was terminated when the solid content acid value (AV: mgKOH / g) became 3 or less to obtain a reactive epoxy carboxylate resin solution. The measurement of the solid content acid value (mgKOH / g) was carried out as a solution and converted to the value in terms of the solid content. Subsequently, 157 g of THPA (1,2,3,6 - tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) as a polybasic acid anhydride (b - 3) and propylene glycol monomethyl ether monoacetate as a solvent were added to the obtained reactive epoxy carboxylate resin solution so that the solid content ratio became 65%. After heating to 100°C, an acid addition reaction was carried out to obtain a reactive polycarboxylic acid resin (II - 3) solution. The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid resin (II - 3) was 100.

[0122] [Synthesis Example 7 (II - 4)] In a 1-L four-necked flask, 305 g of EPPN-503 (manufactured by Nippon Kayaku Co., Ltd., softening point 94 °C, epoxy equivalent 185 g / eq.) as the epoxy resin (b-1), 120 g of acrylic acid (AA) as the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, 3 g of BHT (dibutylhydroxytoluene) as a polymerization inhibitor, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content ratio became 80% by mass, and the mixture was reacted at 100 °C for 24 hours. The reaction was terminated when the solid content acid value (AV: mgKOH / g) became 3 or less, and a reactive epoxy carboxylate resin solution was obtained. The measurement of the solid content acid value (mgKOH / g) was carried out as a solution and converted to the value in terms of the solid content. Subsequently, 158 g of THPA (1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) as the polybasic acid anhydride (b-3) and propylene glycol monomethyl ether monoacetate as a solvent were added to the obtained reactive epoxy carboxylate resin solution so that the solid content ratio became 65%, and after heating to 100 °C, an acid addition reaction was carried out to obtain a reactive polycarboxylic acid resin (II-4) solution. The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid resin (II-4) was 100.

[0123] [Synthesis Example 8 (II-5)] In a 1-L four-necked flask, 336 g of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., softening point 58 °C, epoxy equivalent 276 g / eq.) as the epoxy resin (b-1), 89 g of acrylic acid (AA) as the compound (b-2) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, 3 g of BHT (dibutylhydroxytoluene) as a polymerization inhibitor, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content ratio became 80% by mass, and the mixture was reacted at 100 °C for 24 hours. The reaction was terminated when the solid content acid value (AV: mgKOH / g) became 3 or less, and a reactive epoxy carboxylate resin solution was obtained. The measurement of the solid content acid value (mgKOH / g) was carried out as a solution and converted to the value in terms of the solid content. Subsequently, 158 g of THPA (1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) as a polybasic acid anhydride (b-3) and propylene glycol monomethyl ether monoacetate were added to the obtained reactive epoxy carboxylate resin solution so that the solid content ratio became 65% as a solvent. After heating to 100 °C, an acid addition reaction was carried out to obtain a solution of a reactive polycarboxylic acid resin (II-5). The solid content acid value (AV: mgKOH / g) of the obtained reactive polycarboxylic acid resin (II-5) was 100.

[0124] <Photoinitiator> Irgacure 907 (manufactured by BASF)

[0125] <Photosensitizer> Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)

[0126] <Solvent> Carbitol acetate (CA)

[0127] (Examples 1 to 11 and Comparative Examples 1 to 8) Components (I) to (II) in the compounding amounts shown in Tables 1 and 2, a photoinitiator, a photosensitizer, and a solvent were compounded to prepare photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 8.

[0128] <Evaluation of photosensitive resin composition> The following evaluations were carried out on the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 8. The results are summarized in Tables 1 and 2.

[0129]

Table 1

[0130]

Table 2

[0131] (Compatibility) It was visually confirmed whether the photosensitive resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 8 were uniformly mixed. 〇··Compatible △··Slightly turbid ×··Not compatible at all, and white turbid precipitates were observed

[0132] (Developability) The photosensitive resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 8 were cast on a copper-clad laminate (manufactured by Sumitomo Bakelite, ELC4762), heated at 80 °C for 30 minutes, and a coating film with a film thickness of 20 μm to 25 μm was formed. Then, ultraviolet rays of 500 mJ / cm 2 were irradiated through a step tablet (STOUFFER 21 STEP SENSITIVITY GUIDE manufactured by Kodak). Thereafter, spray development (spray pressure: 0.2 MPa) was performed with a 1% aqueous sodium carbonate solution to remove the resin in the unirradiated portion of the ultraviolet rays. The developability was evaluated by the so-called break time, which is the time until the pattern-shaped portion is completely developed when developing the exposed portion that has passed through the pattern mask. ◎··Break time is within 30 seconds to 60 seconds 〇··Break time is within 61 seconds to 120 seconds ×··Development impossible

[0133] (Evaluation of dielectric properties (dielectric constant, dielectric loss tangent)) For the evaluation of dielectric properties, the varnish was applied and dried on a copper foil so that the thickness after drying with a desktop coater was 50 μm to obtain a resin film (semi-cured). Next, the obtained resin film (semi-cured) was irradiated with UV of 1000 mJ / cm 2 . Further, the copper foil as the support was removed by physical peeling or etching to obtain a resin film for evaluation. Then, a resin film laminated to a length of 60 mm, a width of 2 mm, and a thickness of 50 μm was used as a test piece, and the dielectric properties were measured by the cavity resonator perturbation method. As the measuring instrument, a vector network analyzer ADMSO10c1 manufactured by AET was used, and as the cavity resonator, CP531 (10 GHz band resonator) manufactured by Kanto Electron Application Development Co., Ltd. was used. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0134] (Mechanical property evaluation) First, the photosensitive resin compositions obtained in each of the examples and comparative examples were applied to a copper foil with a thickness of 12 μm to a thickness of about 20 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm to 25 μm. For this film-like photosensitive resin composition, a "super high pressure mercury lamp 500W multi-light" manufactured by USHIO was used, and exposure was performed at a wavelength of 365 nm and an exposure amount of 1000 mJ / cm 2 Thereafter, the copper foil was removed by etching to obtain a cured film.

[0135] Next, the obtained cured film was cut into a length of 50 mm and a width of 5 mm, and the tensile elastic modulus (GPa) and the elongation at break (%) were measured and determined using a tensilon (tensile tester) under the conditions of a chuck distance of 4 cm and a temperature of 23°C at a tensile speed of 5 mm / min.

[0136] (HAST resistance) Each composition was applied onto an Espanex M series (manufactured by Nippon Steel Chemical Co., Ltd.: base imide thickness 25 μm, Cu thickness 18 μm) on which a comb-shaped pattern with L / S = 100 μm / 100 μm was formed to a thickness of 25 μm, and the coating film was dried for 30 minutes with a hot air dryer at 80°C. Then, using an ultraviolet exposure apparatus (manufactured by USHIO: 500W multi-light), exposure was performed at 1000 mJ / cm 2 to cure it, thereby obtaining a test substrate for HAST evaluation. The electrode portion of the obtained substrate was connected by wiring with solder, placed in an environment of 130°C / 85%RH, a voltage of 5.5V was applied, and the time until the resistance value became 1×10^9 Ω or less was measured. ○... 300 hours or more △... 30 to 300 hours ×... 30 hours or less

[0137] As is clear from the results shown in Tables 1 and 2, the photosensitive resin composition of the present invention can be developed with a weak alkaline aqueous solution, and it has been shown that the cured product has high flexibility, dielectric properties, and insulation reliability.

Claims

1. A resin composition for an optical waveguide, comprising a diamine (a-1) derived from dimer acid, a maleimide compound (I) which is a reaction product of maleic anhydride, an epoxy resin (b-1), and a reactive epoxy carboxylate resin which is a reaction product of a compound (b-2) having a polymerizable ethylenic unsaturated group and a carboxy group in one molecule, and a reactive polycarboxylic acid resin (II) which is a reaction product of a polybasic acid anhydride (b-3).

2. The resin composition for an optical waveguide according to Claim 1, wherein the maleimide compound (I) consists of a diamine (a-1) derived from dimer acid, a polybasic acid anhydride (a-2), and maleic anhydride.

3. The resin composition for an optical waveguide according to Claim 2, wherein the polybasic acid anhydride (a-2) has an alicyclic structure.

4. The resin composition for an optical waveguide according to any one of Claims 1 to 3, wherein the maleimide compound (I) is represented by the following general formula (1): 【Chemical 1】 [In formula (1), R １ represents a divalent hydrocarbon group (a) derived from dimer acid, and R ２ represents a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from dimer acid. R ３ represents any one selected from the group consisting of a divalent hydrocarbon group (a) derived from dimer acid and a divalent organic group (b) other than the divalent hydrocarbon group (a) derived from dimer acid. R ４ and R ５ each independently represents one or more organic groups selected from a tetravalent organic group having a monocyclic or condensed polycyclic alicyclic structure and having 6 to 40 carbon atoms, a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are directly or via a crosslinked structure linked to each other, and a tetravalent organic group having 4 to 40 carbon atoms and having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. When the total amount of R ４ and R ５ is 100 mol%, it contains 5 to 95 mol%. m is an integer from 1 to 30, n is an integer from 0 to 30. When m is 2 or more, a plurality of R １ and R ４ may be the same or different from each other. When n is 2 or more, a plurality of R ２ and R ５ may be the same or different from each other.]

5. The resin composition for an optical waveguide according to any one of Claims 1 to 4, wherein the epoxy resin (b-1) is represented by the following general formula (2):

6. 【Chemical 2】 [In formula (2), R ６ represents a hydrocarbon group containing an aromatic ring or an alicyclic skeleton having 1 to 40 carbon atoms, and R ７ may be the same or different and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 40 carbon atoms. Also, x is an integer from 1 to 30.] The resin composition for an optical waveguide according to any one of Claims 1 to 5, comprising a photoinitiator.

7. A cured product of the resin composition for an optical waveguide according to any one of Claims 1 to 6.

8. An optical waveguide having the cured product according to Claim 7. ​ ​

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