Multi-liquid curable resin composition, dry film, cured product, and electronic component

Abstract

Provided is a multi-component curable resin composition which can exhibit stable characteristics such as sensitivity after mixing even after each component liquid is prepared at a high temperature (for example, about 60 DEG C). The multi-pack type curable resin composition comprises, in the same composition liquid: a carboxyl group-containing resin; at least one of primary amine, secondary amine and tertiary amine; and an epoxy compound having a weight average molecular weight of 700 or more.

Description

Technical Field

[0001] This invention relates to multi-component curable resin compositions, dry films, cured products, and electronic components. Background Technology

[0002] In printed circuit boards, solder resist has traditionally been used as a protective material for the circuitry. Examples of compositions that can be used as this protective material include curable resin compositions. These curable resin compositions, for example, incorporate oxime ester-based photopolymerization initiators (i.e., highly photosensitive compounds) to form more precise patterns (specifically, to increase sensitivity during exposure). In recent years, from the viewpoint of quality stability, two-component curable resin compositions have also been proposed (e.g., Patent Documents 1 and 2).

[0003] However, the aforementioned oxime ester-based photopolymerization initiators are highly reactive, therefore their handling requires care. One aspect of this care is the composition manufacturing process.

[0004] To address the issue of quality stability during preservation, a two-component photocurable / thermocurable resin composition was proposed, comprising a composition containing a photopolymerization initiator with oxime bonds and a composition containing a resin with carboxyl groups or a reactive diluent (the invention described in Patent Document 1). Additionally, an alkali-developable curable resin composition was proposed, comprising a two-component composition containing a photopolymerization initiator with oxime bonds and a composition containing an alkali-soluble resin (the invention described in Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2004 / 048434.

[0008] Patent Document 2: Japanese Patent Application Publication No. 2020-140161. Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] In the prior art, such as the inventions described in Patent Documents 1 and 2, each component liquid is specifically prepared using a three-roll mill at a temperature of approximately 40°C. From the viewpoint of expanding the range of preparation methods, it is preferable to use another device (e.g., a bead mill) instead of the conventional three-roll mill for preparing each component liquid. However, when a bead mill is used as another device, the component liquid is prepared at a higher temperature than that in a three-roll mill (e.g., approximately 60°C), and the properties, such as sensitivity, are more likely to change when the component liquids are mixed. In particular, from the viewpoint of productivity such as mixing and dispersion, depending on the curable resin composition, a carboxyl-containing resin and a photopolymerization initiator are sometimes combined in the same component liquid, especially when the photopolymerization initiator is an oxime ester-based photopolymerization initiator, and there is room for improvement.

[0011] The purpose of this invention is to provide a multi-component curable resin composition that exhibits stable properties such as sensitivity after mixing, even when each component liquid is prepared at a high temperature (e.g., around 60°C).

[0012] Methods for solving problems

[0013] The inventors conducted dedicated research and discovered that the above-mentioned problem could be solved by including an epoxy compound with a weight average molecular weight of 700 or more in a composition containing a resin with a carboxyl group and at least one of primary, secondary, and tertiary amines (e.g., an oxime ester-based photopolymerization initiator). This invention was thus completed.

[0014] That is, the above-mentioned objective can be achieved by the multi-liquid curable resin composition according to the present invention.

[0015] A multi-component curable resin composition, characterized in that,

[0016] The multi-component curable resin composition comprises: a carboxyl-containing resin; at least one of primary, secondary, and tertiary amines; and an epoxy compound with a weight-average molecular weight of 700 or more.

[0017] The same composition liquid contains: the carboxyl-containing resin; at least one of the primary amine, secondary amine and tertiary amine; and the epoxy compound with a weight average molecular weight of 700 or more.

[0018] In a preferred embodiment of the multi-component curable resin composition according to the present invention, at least one of the primary amine, secondary amine and tertiary amine comprises an oxime ester-based photopolymerization initiator.

[0019] In another preferred embodiment of the multi-component curable resin composition according to the invention, the multi-component curable resin composition further comprises a photopolymerization initiator different from the oxime ester-based photopolymerization initiator.

[0020] In another preferred embodiment of the multi-component curable resin composition according to the invention, the multi-component curable resin composition contains a greater amount of the oxime ester-based photopolymerization initiator compared to the other photopolymerization initiators.

[0021] In another preferred embodiment of the multi-component curable resin composition according to the present invention, the multi-component curable resin composition further comprises an epoxy compound having a weight-average molecular weight of less than 700, the epoxy compound having a weight-average molecular weight of less than 700 being formulated in a composition liquid different from a composition liquid containing at least one of the primary amine, secondary amine and tertiary amine.

[0022] In addition, the present invention relates to a dry film having a resin layer formed from the curable resin composition.

[0023] In addition, the present invention relates to cured products obtained by curing the multi-component curable resin composition or the resin layer of the dry film.

[0024] In addition, the present invention relates to electronic components having the cured material.

[0025] The effects of the invention

[0026] The multi-component curable resin composition according to the present invention can exhibit stable properties such as sensitivity after mixing, even when each component liquid is prepared at a high temperature (e.g., around 60°C). Detailed Implementation

[0027] The multi-component curable resin composition of the present invention comprises: a carboxyl-containing resin; at least one of a primary amine, a secondary amine, and a tertiary amine; and an epoxy compound with a weight-average molecular weight of 700 or more. It should be noted that the following components are incorporated in the same liquid composition: a carboxyl-containing resin; at least one of a primary amine, a secondary amine, and a tertiary amine; and an epoxy compound with a weight-average molecular weight of 700 or more.

[0028] By further including an epoxy compound with a weight-average molecular weight of 700 or more in a composition containing a carboxyl-containing resin and at least one of primary, secondary, and tertiary amines, the stability of the quality of each composition can be maintained during storage when the carboxyl-containing resin and at least one of primary, secondary, and tertiary amines (e.g., oxime ester-based photopolymerization initiators) are combined in the same composition and then each composition is prepared at a high temperature (e.g., around 60°C) and stored. The reasoning is as follows: Conventionally, when carboxyl-containing resins and at least one of primary, secondary, and tertiary amines are included in the same composition, they react due to the high temperatures applied during manufacturing processes such as kneading, potentially affecting the coating properties during subsequent mixing. However, by further including an epoxy compound with a weight-average molecular weight of 700 or more in the same composition, stable coating properties can be obtained, thus it is believed to have the effect of delaying the aforementioned reaction. However, this is only a speculation and is not limited to this.

[0029] The multi-component curable resin composition of the present invention is composed of at least two or more component liquids (preferably two component liquids), and each component of the multi-component curable resin composition is contained in any one of the at least two or more component liquids to satisfy the following conditions, namely, they are combined in the same component liquid: a carboxyl-containing resin; at least one of primary amine, secondary amine and tertiary amine; and an epoxy compound with a weight average molecular weight of 700 or more.

[0030] The components contained in the multi-component curable resin composition of the present invention will be described below.

[0031] [Carboxyl-containing resin]

[0032] As the carboxyl-containing resin included in the curable resin composition of the present invention, conventionally known resin compounds containing carboxyl groups in their molecules can be used. Furthermore, in the case of preparing an alkaline-developable resin composition, from the perspective of photocurability and developability, a carboxyl-containing photosensitive resin having olefinic unsaturated double bonds in its molecule is more preferred. Moreover, it is preferable that the unsaturated group is derived from acrylic acid or methacrylic acid derivatives. It should be noted that when only a carboxyl-containing resin without olefinic unsaturated double bonds is used, it is necessary to use a photopolymerizable monomer (acrylate component) having two or more olefinic unsaturated groups in its molecule (described later) to make the composition photocurable.

[0033] As a specific example of a carboxyl-containing resin, the following compounds (which can be either oligomers or polymers) are preferred.

[0034] (1) A carboxyl-containing resin obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with compounds containing unsaturated groups such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene.

[0035] (2) A carboxyl-containing urethane resin produced by the addition polymerization reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl-containing diols such as dimethylolpropionic acid and dimethylolbutyric acid and dihydroxy compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylamide polyols, bisphenol A epoxy alkyl adduct diols, and compounds with phenolic hydroxyl and alcoholic hydroxyl groups.

[0036] (3) A carboxyl-containing photosensitive urethane resin produced by the addition polymerization reaction of diisocyanate with (meth)acrylates or their partial anhydride modifications of bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenyl type epoxy resin, etc., carboxyl-containing diol compounds and dihydroxy compounds.

[0037] (4) In the synthesis of the resin in (2) or (3) above, a carboxyl-containing photosensitive urethane resin with a hydroxyl group and one or more methacryloyl groups in the molecule, such as (meth)acrylic acid hydroxyalkyl ester, and (meth)acrylic acid are added to the resin to achieve terminal (meth)acryloylation.

[0038] (5) In the synthesis of the resin in (2) or (3) above, a compound having one isocyanate group and one or more (meth)acryloyl groups in the equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate is added to form a carboxyl-containing photosensitive urethane resin with terminal (meth)acryloylation.

[0039] (6) A photosensitive resin containing carboxyl groups is formed by reacting a difunctional or more multifunctional (solid) epoxy resin with (meth)acrylic acid to add phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and other dicarboxylic anhydride to the hydroxyl groups present in the side chain.

[0040] (7) A carboxyl-containing photosensitive resin is formed by reacting a multifunctional epoxy resin obtained by epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with (meth)acrylic acid and adding a dicarboxylic acid anhydride to the generated hydroxyl groups.

[0041] (8) A carboxyl-containing polyester resin is formed by reacting adipic acid, phthalic acid, hexahydrophthalic acid and other dicarboxylic acids with adipic acid, phthalic acid and hexahydrophthalic acid, etc., and adding phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and other dicarboxylic anhydride to the generated primary hydroxyl group.

[0042] (9) An epoxy compound having multiple epoxy groups in one molecule is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenylethanol, and a monocarboxylic acid containing unsaturated groups, such as (meth)acrylic acid, so that the alcoholic hydroxyl group of the reaction product reacts with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., to obtain a carboxyl-containing photosensitive resin.

[0043] (10) A photosensitive resin containing carboxyl groups is obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with ethylene oxide, propylene oxide or other epoxides, and then reacting the resulting product with a monocarboxylic acid containing unsaturated groups, and then reacting the resulting product with a polyacid anhydride.

[0044] (11) A photosensitive resin containing carboxyl groups is obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with cyclic carbonate compounds such as ethylene carbonate and propylene carbonate, and then reacting the resulting product with a monocarboxylic acid containing unsaturated groups, and then reacting the resulting product with a polyacid anhydride.

[0045] (12) A carboxyl-containing photosensitive resin is formed by further adding a compound having one epoxy group and one or more (meth)acryloyl groups to the resins of (1) to (11) above.

[0046] Among these carboxyl-containing resins, from the viewpoint of low warpage and flexural strength, preferred are (X) carboxyl-containing polyurethane resins, particularly resins in which the isocyanate groups of the isocyanate component (including diisocyanate) are not directly bonded to the benzene ring, and (Y) multifunctional epoxy resins used in the synthesis of the above resins having bisphenol A, bisphenol F, biphenol, biphenylphenolic varnish, bis(xylenol), particularly biphenylphenolic varnish, and their hydrogenated compounds. Furthermore, on the other hand, modified versions of (2), (3), (4), (5), and (12) of the above have urethane bonds in their main chain, which is preferable for warpage. Additionally, resins other than (1), (2), and (8) above, namely (3), (4), (5), (6), (7), (9), (10), (11), and (12), have photosensitive groups in their molecules, thus exhibiting high photoreactivity, which is preferable.

[0047] It should be noted that in this specification, (meth)acrylate refers to the term collectively used for acrylates, methacrylates, and mixtures thereof, and other similar expressions are the same.

[0048] As described above, the carboxyl-containing resin has a large number of free carboxyl groups on the side chains of the main polymer chain, thus becoming crosslinking points during thermosetting. Furthermore, in the case of preparing a photocurable resin composition, it can be developed using a dilute alkaline aqueous solution.

[0049] Furthermore, the acid value of the aforementioned carboxyl-containing resin is in the range of 10–200 mg KOH / g, preferably in the range of 30–200 mg KOH / g, more preferably in the range of 40–200 mg KOH / g, and particularly preferably in the range of 45–120 mg KOH / g. With an acid value of 30 mg KOH / g or higher for the carboxyl-containing resin, the alkali developability of the curable resin composition is good. Additionally, with an acid value of less than 200 mg KOH / g for the carboxyl-containing resin, it is easy to draw good resist patterns.

[0050] Furthermore, the weight-average molecular weight of the aforementioned carboxyl-containing resin varies depending on the resin skeleton, and is generally preferably in the range of 2,000 to 150,000, more preferably in the range of 5,000 to 100,000. A weight-average molecular weight of 2,000 or higher improves surface drying performance and resolution. Conversely, a weight-average molecular weight of 150,000 or lower improves the developability and storage stability of the curable resin composition.

[0051] In the entire composition, the amount of the carboxyl-containing resin, converted from solid content, is preferably 10 to 60% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 60% by mass. When it is less than the above range, the coating strength decreases, which is therefore not preferred. On the other hand, when it is more than the above range, the viscosity of the composition increases, or the coatability decreases, which is also not preferred.

[0052] These carboxyl-containing resins can be used alone or in combination of two or more.

[0053] [At least one of primary amines, secondary amines, and tertiary amines]

[0054] (Oxime ester photopolymerization initiator)

[0055] As at least one of primary, secondary and tertiary amines, for example, oxime ester photopolymerization initiators having groups represented by the following general formula (I) can be cited.

[0056]

[0057] (where R is in the formula) 1This indicates a hydrogen atom, a phenyl group (which may be substituted by an alkyl, phenyl, or halogen atom with 1 to 6 carbon atoms), an alkyl group with 1 to 20 carbon atoms (which may be substituted by more than one hydroxyl group, and may have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group with 5 to 8 carbon atoms, an alkylyl group or a benzoyl group with 2 to 20 carbon atoms (which may be substituted by an alkyl or phenyl group with 1 to 6 carbon atoms), and a phenyl group.

[0058] R 2 This indicates a phenyl group (which may be substituted with an alkyl, phenyl, or halogen atom having 1 to 6 carbon atoms), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, or an alkylyl or benzoyl group having 2 to 20 carbon atoms (which may be substituted with an alkyl or phenyl atom having 1 to 6 carbon atoms).

[0059] Examples of oxime ester-based photopolymerization initiators having groups represented by the above general formula (I) include 2-(acetoxyiminomethyl)thioxanthone represented by the following general formula (II), compounds represented by the following general formula (III), and compounds represented by the following general formula (IV).

[0060]

[0061] (where R is in the formula) 3 This indicates a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxy group has 2 or more carbon atoms, the alkyl group can be replaced by one or more hydroxyl groups, and there can be one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group.

[0062] R 4 R 6 Each of these can independently represent a phenyl group (which may be substituted by an alkyl, phenyl, or halogen atom with 1 to 6 carbon atoms), an alkyl group with 1 to 20 carbon atoms (which may be substituted by more than one hydroxyl group and may have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group with 5 to 8 carbon atoms, or an alkylyl or benzoyl group with 2 to 20 carbon atoms (which may be substituted by an alkyl or phenyl atom with 1 to 6 carbon atoms).

[0063] R 5This indicates a hydrogen atom, a phenyl group (which may be substituted by an alkyl, phenyl, or halogen atom with 1 to 6 carbon atoms), an alkyl group with 1 to 20 carbon atoms (which may be substituted by more than one hydroxyl group and may have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group with 5 to 8 carbon atoms, or an alkylyl or benzoyl group with 2 to 20 carbon atoms (which may be substituted by an alkyl or phenyl group with 1 to 6 carbon atoms).

[0064]

[0065] (where R is in the formula) 7 R 8 and R 13 Each can be independently represented as an alkyl group having 1 to 12 carbon atoms.

[0066] R 9 R 10 R 11 and R 12 Each can be independently represented by an alkyl group having 1 to 6 hydrogen atoms.

[0067] M represents O, S, or NH.

[0068] p and q independently represent integers from 0 to 5.

[0069] Oxime ester photopolymerization initiators having groups represented by the above general formula (II) are preferred because they have good initiator efficiency and a small amount is effective in improving sensitivity. Therefore, less venting is required during heat treatment after forming the resist film, which is effective in reducing film warpage.

[0070] Among the above-mentioned oxime ester-based photopolymerization initiators, 2-(acetoxyiminomethyl)thioxanthone-9-one represented by general formula (II), ethyl ketone represented by general formula (III), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), and compounds represented by general formula (IV) are more preferred. Commercially available examples include IrgacureOXE02 and IrgacureOXE04 manufactured by BASF Japan. The amount of the above-mentioned oxime ester-based photopolymerization initiator, calculated in terms of solids content, is preferably 0.01 to 30 parts by weight relative to 100 parts by weight of the carboxyl-containing resin, and more preferably, a range of 0.5 to 20 parts by weight is suitable.

[0071] From a sensitivity / resolution point of view, it is preferable to use the oxime ester-based photopolymerization initiator in greater proportion than other photopolymerization initiators different from the aforementioned oxime ester-based photopolymerization initiators (specifically, photopolymerization initiators containing nucleophilic groups and those without nucleophilic groups, as described below). Specifically, the ratio of the oxime-based photopolymerization initiator to other photopolymerization initiators is preferably 1:0.01 to 1:20, more preferably 1:0.02 to 1:10, further preferably 1:0.02 to 1:1, and particularly preferably 1:0.02 to 1:0.7.

[0072] (Photopolymerization initiators containing nucleophilic groups)

[0073] As any one of primary, secondary, and tertiary amines, for example, photopolymerization initiators containing nucleophilic groups that differ from the above-mentioned oxime ester-based photopolymerization initiators (e.g., α-aminoacetophenone-based photopolymerization initiators having groups represented by the following general formula (V)).

[0074]

[0075] (where R is in the formula) 14 and R 15 Each can be independently represented as an alkyl or arylalkyl group having 1 to 12 carbon atoms.

[0076] R 16 and R 17 Each of these groups independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or two bonded cyclic alkyl ether groups.

[0077] Examples of α-aminoacetophenone-based photopolymerization initiators having groups represented by the above general formula (V) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone. Commercially available examples include Omnirad 369 and Omnirad 379 manufactured by IGM Resins. The amount of the above-mentioned α-aminoacetophenone-based photopolymerization initiator, calculated in terms of solids content, is preferably 0.1 to 80 parts by weight relative to 100 parts by weight of the carboxyl-containing resin, and more preferably, a range of 2 to 50 parts by weight is suitable.

[0078] The above-mentioned photopolymerization initiators can be used alone or in combination of two or more.

[0079] Oxime ester photopolymerization initiators having groups represented by the above general formula (V) are preferred because they have good initiator efficiency and a small amount is effective in improving sensitivity. Therefore, less venting is required during heat treatment after forming the resist film, which is effective in reducing film warpage.

[0080] (Catalysts containing nucleophilic groups)

[0081] Catalysts containing nucleophilic groups can be cited as examples of at least one of primary, secondary, and tertiary amines. Examples of catalysts containing nucleophilic groups include, for instance, imidazole derivatives such as imidazole, 2-methylimidazolium, 2-ethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 4-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; and hydrazine compounds such as adipate dihydrazide and sebacate dihydrazide. In particular, these are not limited to these; any catalyst that is a thermosetting catalyst for epoxy resins or oxetane compounds, or that promotes the reaction of at least one of epoxy groups and oxetane groups with a carboxyl group, can be used alone or in combination of two or more. Alternatively, S-triazine derivatives such as guanidine, acetylguanidine, benzoguanidine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct can also be used. Preferably, these compounds, which also function as adhesion promoters, are used in combination with the above-mentioned thermosetting catalyst.

[0082] The above compounds can be used alone or in combination of two or more. Examples of commercially available products include CUA-4 (primary amine) manufactured by Kumiai Chemical Industry Co., Ltd., DMP-30 (tertiary amine) manufactured by Tribon Co., Ltd., and melamine (primary amine) manufactured by Nissan Chemical Co., Ltd.

[0083] The amount of catalyst containing nucleophilic functional groups is sufficient in a normal proportion, preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, in terms of solid content, relative to 100 parts by weight of the carboxyl-containing resin mentioned above.

[0084] Relative to 100 parts by weight of the carboxyl-containing resin, the amount of at least one of the primary, secondary, and tertiary amines, calculated in terms of solid content, is preferably 0.1 to 20 parts by weight, and more preferably, a range of 0.1 to 12 parts by weight is appropriate. If the amount of at least one of the primary, secondary, and tertiary amines is 0.1 parts by weight or more, the photocurability on copper is improved, and coating properties such as chemical resistance are also improved, which is therefore preferred. On the other hand, if it is less than 20 parts by weight, the light absorption at the surface of the solder resist coating is appropriate, and there is a tendency for improved deep curing properties, which is also preferred.

[0085] [Epoxy compounds with a weight-average molecular weight of 700 or higher]

[0086] Examples of epoxy compounds with a weight-average molecular weight of 700 or more include bisphenol A type epoxy compounds, phenolic varnish type epoxy compounds, and hydrogenated bisphenol A type epoxy compounds. The lower limit of the weight-average molecular weight of these epoxy compounds is 700 or more, preferably 800 or more, and more preferably 850 or more. The upper limit of the weight-average molecular weight of these epoxy compounds is preferably 5000 or less, more preferably 3000 or less. These lower and upper limits can be combined arbitrarily. The weight-average molecular weight of the epoxy compound can be determined, for example, by gel permeation chromatography (GPC). It should be noted that epoxy compounds with a weight-average molecular weight within the above range can be obtained based on the technical knowledge of those skilled in the art.

[0087] The aforementioned epoxy compounds with a weight-average molecular weight of 700 or higher can be used alone or in combination of two or more. Examples of commercially available products include N-870 manufactured by DIC Corporation, P201 manufactured by Nippon Kayaku Co., Ltd., and ST-5100 manufactured by Nippon Steel Chemical Materials Co., Ltd.

[0088] The content of the epoxy compound with a weight average molecular weight of 700 or more, relative to the entire composition, is preferably 1 to 100% by mass, more preferably 5 to 60% by mass, calculated as solids content.

[0089] [Epoxy compounds with a weight average molecular weight of less than 700]

[0090] The multi-component curable resin composition of the present invention may also include an epoxy compound with a weight-average molecular weight of less than 700. Examples of epoxy compounds with a weight-average molecular weight of less than 700 include, for example, hydrogenated resin-type epoxy compounds, biphenyl-type epoxy compounds, and bisphenol A-type epoxy compounds. The lower limit of the weight-average molecular weight of these epoxy compounds is preferably 5 or more, and more preferably 10 or more. The upper limit of the weight-average molecular weight of this epoxy compound is less than 700. These lower and upper limits can be combined arbitrarily. The weight-average molecular weight of this epoxy compound can be obtained, for example, by the same determination method described in the description of epoxy compounds with a weight-average molecular weight of 700 or more. It should be noted that epoxy compounds with a weight-average molecular weight within the above range can be obtained through the technical knowledge of those skilled in the art.

[0091] The aforementioned epoxy compounds with a weight-average molecular weight of less than 700 can be used alone or in combination of two or more. Commercially available examples include YX-8034 and jER834 manufactured by Mitsubishi Chemical Corporation.

[0092] The content of the epoxy compound with a weight average molecular weight of less than 700, relative to the entire composition, is preferably 1 to 100% by mass, more preferably 5 to 60% by mass, calculated as solids content.

[0093] The aforementioned epoxy compounds with a weight-average molecular weight of less than 700 may promote reactions with at least one of primary, secondary, and tertiary amines. Therefore, it is preferred to formulate them in a different compositional solution than that containing at least one of the aforementioned primary, secondary, and tertiary amines.

[0094] [(Meth)acrylate component]

[0095] The photopolymerizable monomer ((meth)acrylate component) is a substance that is photocured by irradiation with active energy rays, making the multi-liquid type curable resin composition of the present invention insoluble or conducive to insolubility in alkaline aqueous solutions. Examples of such compounds include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyacrylates of polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and trihydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyacrylates of phenoxyacrylates, bisphenol A diacrylates, and their ethylene oxide adducts or propylene oxide adducts; polyacrylates of glycidyl ethers such as diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; melamine acrylates; and at least one of the various methacrylates corresponding to the above-mentioned acrylates. It should be noted that in this specification, (meth)acrylate refers to a general term encompassing acrylates, methacrylates, and mixtures thereof, and other similar expressions are also applicable.

[0096] Furthermore, examples include epoxy-based acrylate resins formed by reacting acrylic acid with multifunctional epoxy resins such as cresol-phenolic varnish-type epoxy resins, and epoxy-based urethane acrylate compounds formed by reacting hydroxyl acrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate with the hydroxyl groups of the epoxy-based acrylate resin. Such epoxy-based acrylate resins can improve photocurability without reducing touch-drying properties.

[0097] The above-mentioned compounds can be used alone or in combination of two or more. Examples of commercially available products include DPCA-60 manufactured by Nippon Kayaku Co., Ltd., and DPHA manufactured by Kyoei Chemical Co., Ltd.

[0098] Relative to 100 parts by weight of the aforementioned carboxyl-containing resin, the amount of this (meth)acrylate component, calculated in terms of solid content, is 5 to 80 parts by weight, more preferably 10 to 40 parts by weight. When the amount is 5 parts by weight or more, the photocurability is improved, and alkaline development after irradiation with active energy rays makes it easier to form patterns, which is therefore preferable. On the other hand, when it is less than 80 parts by weight, it is preferable from the viewpoint of obtaining a suitable surface hardness of the coating film.

[0099] [Photopolymerization initiators without nucleophilic groups]

[0100] The multi-component curable resin composition of the present invention may also contain a photopolymerization initiator that does not contain nucleophilic groups (nucleophilic functional groups). As a photopolymerization initiator that does not contain nucleophilic functional groups, it is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having groups represented by the following formula (VI).

[0101]

[0102] (where R is in the formula) 18 and R 19 Each of the following groups independently represents a straight-chain or branched alkyl, cyclohexyl, cyclopentyl, aryl, or aryl group substituted with a halogen atom, alkyl group, or alkoxy group, having 1 to 10 carbon atoms, wherein R 10 and R 11 One of them can represent the RC (=O)- group (here, R is a hydrocarbon group with 1 to 20 carbon atoms).

[0103] Examples of acylphosphine oxide photopolymerization initiators having groups represented by the above general formula (VI) include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.

[0104] The above compounds can be used alone or in combination of two or more. Commercially available examples include Omnirad 819 and Omnirad 1173 manufactured by IGM Resins.

[0105] Acylphosphine oxide initiators having groups represented by the above general formula (VI) exhibit the best light transmittance in terms of photobleaching performance and are also effective in flame retardancy.

[0106] Relative to 100 parts by weight of the carboxyl-containing resin, the amount of the photopolymerization initiator without nucleophilic functional groups described above, converted to solids, is 0.1 to 80 parts by weight, preferably in the range of 2 to 50 parts by weight.

[0107] If the amount of photopolymerization initiator without nucleophilic functional groups is 0.1 parts by mass or more, the photocurability on copper becomes sufficient, and the coating properties such as chemical resistance are improved, which is therefore preferred. On the other hand, if it is less than 80 parts by mass, the light absorption at the surface of the solder resist coating without nucleophilic functional groups is moderate, and there is a tendency to improve deep curing performance, which is also preferred.

[0108] [Flame retardant]

[0109] The multi-component curable resin composition of the present invention may also contain a flame retardant. A flame retardant may be incorporated to impart flame retardancy to the cured product obtained after curing the curable composition. Preferably, the flame retardant is one that can improve the flame retardancy of the cured product without impairing its coatability, resolution, or warpage. In particular, the flame retardant used in the present invention has the advantage of uniformly improving post-exposure warpage, tackiness, transparency, and storage stability.

[0110] It should be noted that compounds that are at least one of the primary, secondary, and tertiary amines mentioned above are excluded from flame retardants.

[0111] [Other ingredients]

[0112] In the multi-component curable resin composition of the present invention, without departing from the purpose of the present invention, additives may be further added as other components as needed.

[0113] Examples of such components include, for example, colorants, solvents, thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / mildew inhibitors, leveling agents, tackifiers, adhesion promoters, thixotropic promoters, photoinitiators, sensitizers, photoalkalizing agents, thermoplastic resins, elastomers, urethane beads, and other organic fillers, inorganic fillers, release agents, surface treatment agents, dispersants, dispersing aids, surface modifiers, stabilizers, phosphors, cellulose resins, etc.

[0114] [Method for manufacturing and using the multi-component curable resin composition of the present invention]

[0115] The multi-component curable resin composition of the present invention can be prepared by mixing and dispersing each component liquid containing any one of the various components in a predetermined amount at a high temperature (e.g., around 60°C) before use, for example, using a bead mill, and then mixing these component liquids together before use.

[0116] The curable resin composition of the present invention can be used in liquid form or by dry film formation.

[0117] [Dry film]

[0118] The dry film of the present invention can be manufactured by coating a first film with the curable resin composition of the present invention, drying it, and forming a resin layer as a dry coating film. If necessary, a second film can be laminated onto the resin layer.

[0119] The first film refers to a film that functions as a resin layer supporting a dry film, and is formed by coating a curable resin composition with the resin layer. Examples of first films include polyester films (such as polyethylene terephthalate and polyethylene naphthalate), polyimide films, polyamide-imide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, polystyrene films, etc., all made of thermoplastic resins, as well as surface-treated paper. From the viewpoints of heat resistance, mechanical strength, and operability, polyester films are preferred. The thickness of the first film is not particularly limited and can be appropriately selected within a range of approximately 10 to 150 μm depending on the application. A demolding treatment can be performed on the surface of the first film where the resin layer is applied. Furthermore, sputtering or copper foil can be formed on the surface of the first film where the resin layer is applied.

[0120] The second film refers to the side of the resin layer opposite to the first film, which is provided to prevent dust and other contaminants from adhering to the surface of the dry film and to improve operability. Examples of the second film include films made of thermoplastic resins as exemplified in the first film, as well as surface-treated paper, with polyester films, polyethylene films, and polypropylene films being preferred. The thickness of the second film is not particularly limited and can be appropriately selected in the range of approximately 10 to 150 μm depending on the application. A demolding treatment can be performed on the side of the second film where the resin layer is located.

[0121] [cured material]

[0122] The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention.

[0123] To form a cured product using the multi-component curable resin composition of the present invention, the component liquids are first mixed. There are no particular limitations as long as the component liquids are two or more, but two liquids are preferred. As a mixing method, stirring with a stirring blade such as a dissolver is preferred. Then, the mixed composition is coated onto a substrate, and the resin layer obtained after evaporating and drying the solvent is exposed (light irradiation), thereby curing the exposed portion (the portion after light irradiation). Specifically, the pattern is selectively exposed using active energy rays or a direct laser exposure machine using a patterned photomask in a contact or non-contact manner, and the unexposed portion is developed with an alkaline aqueous solution (e.g., a 0.3–3% by mass sodium carbonate aqueous solution) to form a resist pattern. Furthermore, by heating to a temperature of approximately 100–220°C for heat curing (post-curing), a cured film (cured product) with excellent properties such as heat resistance, chemical resistance, moisture resistance, adhesion, and electrical properties can be formed.

[0124] In the case of a dry film, either the first film or the second film is peeled off from the dry film, heated and laminated onto a circuit board with a circuit pattern, and then thermo-cured. Thermo-curing can be performed in an oven or by applying pressure with a hot plate. When laminating the circuit board and the dry film of the present invention, or by applying pressure with a hot plate, copper foil or the circuit board can also be laminated simultaneously. Patterns and through-holes are formed at positions corresponding to predetermined locations on the circuit board using laser irradiation or a drill bit, exposing the circuit wiring, thereby enabling the manufacture of a printed wiring board. If there are residual components (stains) on the circuit wiring within the patterns or through-holes that have not been completely removed, a decontamination process is performed. Any residue remaining in either the first or second film can be peeled off after lamination, after thermo-curing, after laser processing, or after the decontamination process.

[0125] [Formation and cured product of coating using a curable resin composition]

[0126] The formation of the cured coating and the cured product using the multi-component curable resin composition of the present invention can be carried out as described below.

[0127] First, in order to form a cured coating using the multi-component curable resin composition of the present invention, the component liquids are mixed. There are no particular limitations as long as the component liquids are two or more, but two liquids are preferred. As a mixing method, stirring with a stirring blade such as a dissolver is preferred. Then, the multi-component curable resin composition is coated onto a substrate, and the resin layer obtained after evaporating and drying the solvent is exposed (light irradiation), thereby curing the exposed portion (the portion exposed to light). Specifically, the pattern is selectively exposed using active energy rays or directly using a laser direct exposure machine, either by forming a patterned photomask using a contact or non-contact method. Then, the unexposed portion is developed using an alkaline aqueous solution (e.g., a 0.3–3% by mass sodium carbonate aqueous solution), thereby forming a resist pattern. Further, it is heated to a temperature of approximately 100–220°C for thermal curing (post-curing), thereby forming a cured coating or other cured product with excellent properties such as heat resistance, chemical resistance, moisture resistance, adhesion, and electrical properties.

[0128] Here, for the multi-liquid curable resin composition of the present invention, for example, after adjusting the viscosity to a suitable coating method using an organic solvent, and coating it onto a substrate by methods such as dip coating, flow coating, roller coating, rod coating, screen printing, curtain coating, etc., the organic solvent contained in the composition is evaporated and dried (pre-dried) at a temperature of about 60 to 100°C, thereby forming a surface-dried resin layer.

[0129] As substrates, in addition to printed wiring boards or flexible printed wiring boards with circuits pre-formed from copper, examples include copper-clad laminates of all grades (FR-4, etc.) made of materials such as paper phenolic resin, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth / non-woven epoxy, glass cloth / paper epoxy resin, synthetic fiber epoxy, fluoropolymer-polyethylene-polyphenylene ether, and polyphenylene ether-cyanate ester, as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, and wafer boards.

[0130] Evaporative drying or thermosetting can be performed using, for example, hot air circulating drying ovens, IR ovens, hot plates, convection ovens, etc. (using a heat source with a steam-based air heating method, a method of hot air convection contact within the dryer and a method of spraying from nozzles onto the support).

[0131] As an exposure machine for irradiating active energy rays, any device equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, or mercury short-arc lamp that irradiates ultraviolet light in the range of 350–450 nm is acceptable. Furthermore, a direct drawing device (e.g., a laser direct imaging device that directly draws images using laser light from CAD data from a computer) can also be used. The light source or laser source for the direct drawing machine can be a light source with a maximum wavelength in the range of 350–410 nm. The exposure dose used to form the image varies depending on the film thickness, and can typically be set from 20 to 2000 mJ / cm². 2 Preferably, it can be set to 20–1500 mJ / cm 2 Within the range.

[0132] As a developing method, immersion, spraying, spraying, brushing, etc. can be used. As a developing solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.

[0133] The multi-component curable resin composition of the present invention is preferably used to form a cured film on a printed wiring board, more preferably to form a permanent coating, and even more preferably to form a solder resist, an interlayer insulating layer, or a cover layer. Furthermore, it is particularly suitable for flexible printed wiring boards requiring properties such as flexural strength.

[0134] [Specific methods for photopolymerization initiators in cured products]

[0135] The components of photopolymerization initiators in the cured material can be identified and quantified, for example, by the following methods.

[0136] As a method for identification, for example, well-known Fourier transform infrared spectrometers (FT-IR) and ultraviolet-visible spectrophotometers can be used for identification. Preferably, a method for identifying the photopolymerization initiator component in the cured material is to measure the infrared absorption spectrum of the cured material using a Fourier transform infrared spectrometer (FT-IR).

[0137] As a method for identification and quantification, quantification can be performed using, for example, well-known ultraviolet-visible spectrophotometers and Fourier transform infrared spectrophotometers (FT-IR). Preferably, a method for identifying and quantifying the photopolymerization initiator component in the cured product is described using an ultraviolet-visible spectrophotometer to obtain UV spectra. For example, oxime ester-based photopolymerization initiators have strong absorption in the 320 nm to 350 nm range, thus allowing for quantification in this region.

[0138] [Electronic Components]

[0139] Furthermore, the present invention also provides electronic components having the aforementioned cured material. By using the multi-component curable resin composition of the present invention, electronic components with high quality, durability, and reliability are provided. It should be noted that, in the present invention, electronic components refer to components used in electronic circuits, including not only active components such as printed circuit boards, transistors, light-emitting diodes, and laser diodes, but also passive components such as resistors, capacitors, inductors, and connectors.

[0140] Example

[0141] The present invention will be specifically described below with examples and comparative examples, but the present invention is not limited to the following examples.

[0142] (synthesis example)

[0143] (Synthesis of carboxyl-containing resin A)

[0144]

[0145] 380 parts of bisphenol F type epoxy resin (epoxy equivalent 950 g / eq, softening point 85℃) with X being CH2 and an average degree of polymerization n of 6.2 in the above general formula (1) and 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide. Then, 60.9 parts of 98.5% NaOH were added at 70℃ for 100 minutes with stirring. After addition, the reaction was carried out at 70℃ for 3 hours. After the reaction was completed, 250 parts of water were added for washing. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation from the oil layer under reduced pressure. The reaction product containing residual by-product salts and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and then 10 parts of 30% NaOH were added. The reaction was carried out at 70℃ for 1 hour. After the reaction was completed, 200 parts of water were used for two washings. After oil-water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain epoxy resin (a) with an epoxy equivalent of 310 g / eq and a softening point of 69 °C. For the obtained epoxy resin (a), based on the epoxy equivalent, approximately 5 of the 6.2 alcoholic hydroxyl groups in the aforementioned bisphenol F type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were added to a flask, heated to 90 °C, and stirred to dissolve. The resulting solution was temporarily cooled to 60 °C, and 72 parts (1 mol) of acrylic acid, 0.5 parts of methyl hydroquinone, and 2 parts of triphenylphosphine were added. The mixture was heated to 100 °C and reacted for approximately 60 hours to obtain a reactant with an acid value of 0.2 mg KOH / g. 140 parts (0.92 mol) of tetrahydrophthalic anhydride were added to this reactant, and the mixture was heated to 90 °C to react, yielding a resin solution containing carboxyl-containing resin A. The obtained resin solution had a solids content of 65.0% and an acid value (mgKOH / g) of 100. The weight-average molecular weight (Mw) was 15000.

[0146] (Examples 1-7 and Comparative Examples 1-2)

[0147] The various components shown in Table 1 below were mixed and dispersed using a bead mill in the proportions shown in Table 1 (unit: parts by mass) (temperature of the first and second component liquids = approximately 60°C; rotation speed 700–1400 rpm, 3–12 minutes, spray volume 5%–40%, bead diameter 0.1 mm–1.0 mm) to prepare the first and second component liquids constituting the two-component curable resin composition.

[0148] Table 1

[0149]

[0150] Carboxyl-containing resin A: The carboxyl-containing resin A obtained in the above "Synthesis of carboxyl-containing resin A".

[0151] N-870: N-870 (bisphenol A type epoxy compound) manufactured by DIC Corporation [equivalent 200; weight average molecular weight 1000-2000].

[0152] P201: P201 (phenolic varnish-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd. [equivalent 200; weight-average molecular weight 1000-2000].

[0153] ST-5100: Manufactured by Nippon Steel Chemical Materials Co., Ltd. (hydrogenated bisphenol A type epoxy compound) [equivalent 450; weight average molecular weight 900].

[0154] 834: JER834 (bisphenol A type epoxy compound) manufactured by Mitsubishi Chemical Corporation [equivalent 250; weight average molecular weight 500].

[0155] DPCA-60: KAYARAD DPCA-60 (caprolactone-modified acrylate) manufactured by Nippon Kayaku Co., Ltd.

[0156] OXE02: Irgacure OXE02 (oxime ester photopolymerization initiator) manufactured by BASF Japan; Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)).

[0157] OXE04: Irgacure OXE04 (oxime ester photopolymerization initiator) manufactured by BASF Japan.

[0158] 369: Omnirad 369 (α-aminoalkylphenyl ketone, photopolymerization initiator) manufactured by IGM Resins; 2-benzyl-2-(dimethylamino)-4′-morpholinobutyroylbenzene.

[0159] 379: Omnirad 379EG (α-aminoalkylphenyl ketone, photopolymerization initiator) manufactured by IGM Resins; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-ylphenyl)-but-1-one.

[0160] CUA-4 (primary amine): CUA-4 (trimethylene-bis(4-aminobenzoate)) manufactured by Kumiai Chemical Industry Co., Ltd.

[0161] 2E4MZ (Secondary Amine): 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd.

[0162] DMP-30 (tertiary amine): DMP-30 (2,4,6-tris(dimethylaminomethyl)phenol) manufactured by Tri-Bond Co., Ltd.

[0163] Melamine: Melamine (primary amine) manufactured by Nissan Chemical Co., Ltd.

[0164] TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0165] 819: Omnirad 819 (bisacylphosphine oxide initiator) manufactured by IGM Resins; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0166] 1173: Omnirad 1173 (photopolymerization initiator, α-hydroxyacetophenone) manufactured by IGM Resins; 2-hydroxy-2-methyl-1-phenylpropanone.

[0167] YX-8034: Mitsubishi Chemical Co., Ltd. (biphenyl-type epoxy compound) [equivalent 270; weight average molecular weight 540].

[0168] DPHA: Dipentaerythritol hexaacrylate.

[0169] 2MZ-A (Primary Amine): 2MZ-A (2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine) manufactured by Shikoku Chemical Industry Co., Ltd.

[0170] (Coating preparation)

[0171] The first and second component liquids of Examples 1-7 and Comparative Examples 1-2 were thoroughly mixed in a ratio of main agent: curing agent = 1:1 using a dissolving device (15 minutes at room temperature, 800 rpm). The mixtures were then applied to a glass substrate using an applicator to achieve a film thickness of 10 μm after drying. The film was then dried at 80°C for 30 minutes in a hot air circulating drying oven to produce an initial coating (without standing at 50°C).

[0172] In addition, a first component solution and a second component solution were prepared separately. For the samples that were placed in a constant temperature bath at 50°C for 7 days, a coating film was also made by mixing and drying in the same way as above.

[0173] (Sensitivity of the mixed curable resin composition)

[0174] As described above, the first and second component solutions, prepared by mixing and dispersing using a bead mill, were thoroughly mixed in a 1:1 ratio using a dissolver (800 rpm, 15 minutes at room temperature). The resulting film was then coated onto the entire surface of the etch-out substrate to achieve a dried film thickness of 30 μm. The film was dried at 80°C for 30 minutes to ensure the steptablet (Kodak No. 2) adhered tightly to each coating. An exposure machine using a metal halide lamp (ORC MANUFACTURING CO.,LTD. HMW-680-GW20) was used at 500 mJ / cm². 2 Exposure was performed using a 1.0% by mass sodium carbonate aqueous solution, with a jet pressure of 0.2 MPa and a development temperature of 30°C for 1 minute. The sensitivity (hereinafter referred to as sensitivity 1) was obtained by measuring the residual number and gloss number from a step gray film (Kodak No. 2).

[0175] On the other hand, the first and second component liquids constituting a two-component curable resin composition were prepared by mixing the various components shown in Table 1 in the proportions (unit: parts by mass) using a three-roll mill. The first and second component liquids were thoroughly mixed in a 1:1 ratio using a dissolver (800 rpm, 15 minutes at room temperature), and then coated onto the entire surface of an etched substrate to a dried film thickness of 30 μm. The mixture was dried at 80°C for 30 minutes to allow the step gray film (Kodak No. 2) to adhere tightly to each coating film. An exposure machine with a metal halide lamp (HMW-680-GW20, Okko Co., Ltd.) was used at 500 mJ / cm². 2 Exposure was performed using a 1.0% by mass sodium carbonate aqueous solution, developed at 30°C for 1 minute with a jet pressure of 0.2 MPa. The sensitivity (hereinafter referred to as sensitivity 2) was obtained by measuring the residual order and gloss order from a step-gray film (Kodak No. 2). Sensitivity 1 and sensitivity 2 were compared and evaluated according to the following criteria.

[0176] 〇: Sensitivity remains unchanged (for residual sensitivity and gloss sensitivity, the deviation between sensitivity 1 and sensitivity 2 is less than ±1 order).

[0177] ×: Sensitivity decreased (for residual sensitivity and gloss sensitivity, the deviation between sensitivity 1 and sensitivity 2 is greater than ±2 orders).

[0178] <Resolution of the mixed curable resin composition>

[0179] The first and second component solutions were thoroughly mixed using a dissolver (800 rpm, 15 minutes) to obtain a two-component curable resin composition. The mixed curable resin composition was then screen-printed onto the entire surface of a full copper substrate to achieve a 30 μm film thickness after drying. The substrate was dried at 80°C for 30 minutes and then exposed to optimal exposure using a negative film with an L / S ratio of 100 μm / 50 μm and a metal halide lamp exposure machine (HMW-680-GW20, Okko Co., Ltd.). After development, the residual lines and shape at 70 μm to 100 μm were evaluated according to the following criteria. It should be noted that, for the optimal exposure, the above-mentioned dried coating surface is exposed using an exposure machine equipped with a metal halide lamp as the light source and a stepped gray film (Kodak No. 2). The exposure level is set to the pattern of the residual stepped gray film after developing with a 1.0% by mass sodium carbonate aqueous solution at a jet pressure of 0.2 MPa and a temperature of 30°C for 1 minute, which is 6 to 7 steps.

[0180] ◎: 70μm line residue, good shape.

[0181] 〇: 100μm line residue, good shape.

[0182] ×: No residue of 100μm line.

[0183] <Resistance to Electroless Gold Plating of the Mixed Curable Resin Composition>

[0184] The first and second component solutions were thoroughly mixed using a dissolver (800 rpm, 15 minutes) to obtain a mixed curable resin composition. Then, the mixed curable resin composition was screen-printed onto the entire surface of a full copper substrate to achieve a cured film thickness of 30 μm. The substrate was dried at 80°C for 30 minutes and then exposed to the substrate using a metal halide lamp exposure machine with an L / S ratio of 100 μm / 50 μm and the optimal exposure level. It should be noted that for the optimal exposure level, the dried coating surface was exposed using a metal halide lamp-mounted exposure machine (HMW-680-GW20, Okko Co., Ltd.) as the light source and a step-gray film (Kodak No. 2). The exposure level was set to achieve a pattern of 6-7 steps in the step-gray film after development at 30°C for 1 minute using a 1.0% by mass sodium carbonate aqueous solution at a jet pressure of 0.2 MPa. Then, the substrate was heat-treated at 150°C for 60 minutes in a hot air circulating drying oven to obtain an evaluation substrate with a cured coating. Using commercially available electroless nickel plating baths and electroless gold plating baths, the evaluation substrate was plated at a nickel thickness of 3 μm and a gold thickness of 0.03 μm. The presence or absence of resist layer peeling and plating penetration was evaluated by tape peeling. The judgment criteria are as follows.

[0185] ○: No peeling was observed.

[0186] ×: Delamination occurred after plating.

[0187] <Welding heat resistance of the mixed curable resin composition>

[0188] The first and second component solutions were thoroughly mixed using a dissolver (800 rpm, 15 minutes) to obtain a two-component curable resin composition. The mixed curable resin composition was then screen-printed onto the entire surface of a full copper substrate to achieve a cured film thickness of 30 μm. The substrate was dried at 80°C for 30 minutes and then exposed to the substrate using a metal halide lamp exposure machine with an L / S ratio of 100 μm / 50 μm and the optimal exposure level. It should be noted that for the optimal exposure level, the dried coating surface was exposed using a metal halide lamp-mounted exposure machine (HMW-680-GW20, Okko Co., Ltd.) as the light source and a step-gray film (Kodak No. 2). The exposure level was set to achieve a pattern of 6-7 steps in the step-gray film after development at 30°C for 1 minute using a 1.0% by mass sodium carbonate aqueous solution at a jet pressure of 0.2 MPa. Then, the substrate is heat-treated at 150°C for 60 minutes in a hot air circulating drying oven to obtain an evaluation substrate with a cured coating. The evaluation substrate coated with rosin-based flux is immersed in a solder bath set to 260°C, and after washing the flux with modified alcohol, the bulging / peeling of the resist layer is visually evaluated. The judgment criteria are as follows.

[0189] ○: No peeling was observed after immersion for 10 seconds.

[0190] ×: Immersion for 10 seconds at a time resulted in bulging and peeling of the resist layer.

[0191] Productivity

[0192] Using the proportions (unit: parts by mass) shown in Table 1 above, the various components shown in Table 1 were mixed and dispersed using a bead mill (temperature of the first and second component liquids = approximately 60°C; rotation speed 700–1400 rpm, 3–12 minutes, spray volume 5%–40%, bead diameter 0.1 mm–1.0 mm) to prepare the first and second component liquids constituting a two-component curable resin composition. The mixing and dispersion times were measured and evaluated as described below.

[0193] ○: The first and second components of the liquid were mixed and dispersed within 15 minutes.

[0194] △: Either the first component liquid or the second component liquid is mixed and dispersed within a time of more than 15 minutes and less than 30 minutes.

[0195] ×: Both the first and second component solutions were mixed and dispersed for more than 30 minutes.

[0196] <Results>

[0197] The results for sensitivity, resolution, resistance to electroless gold plating, solder heat resistance, and productivity are shown in Table 2 below.

[0198] Table 2

[0199]

[0200] Based on the above results, it can be seen that the two-component curable resin compositions of Examples 1-7 exhibit good sensitivity, resolution, resistance to electroless gold plating, and solder heat resistance after mixing. On the other hand, the two-component curable resin compositions of Comparative Examples 1-2 show poor sensitivity, resolution, and resistance to electroless gold plating after mixing.

[0201] Furthermore, based on the productivity results, it can be seen that if a photopolymerization initiator is also added to the same composition liquid as the carboxyl-containing resin, the mixing and dispersion time becomes faster and the productivity is better.

Claims

1. A multi-component curable resin composition, characterized in that, The multi-component curable resin composition comprises: a carboxyl-containing resin; at least one of primary, secondary, and tertiary amines; and an epoxy compound with a weight-average molecular weight of 700 or more. The same composition liquid contains: the carboxyl-containing resin; at least one of the primary amine, secondary amine and tertiary amine; and the epoxy compound with a weight average molecular weight of 700 or more.

2. The multi-component curable resin composition according to claim 1, wherein, At least one of the primary, secondary, and tertiary amines contains an oxime ester-based photopolymerization initiator.

3. The multi-component curable resin composition as described in claim 2, wherein, The multi-component curable resin composition also contains other photopolymerization initiators different from the oxime ester-based photopolymerization initiators.

4. The multi-component curable resin composition according to claim 3, wherein, Compared to the other photopolymerization initiators, the multi-component curable resin composition contains more of the oxime ester-based photopolymerization initiator.

5. The multi-component curable resin composition according to claim 1, wherein, The multi-component curable resin composition further comprises an epoxy compound with a weight-average molecular weight of less than 700, wherein the epoxy compound with a weight-average molecular weight of less than 700 is formulated in a composition liquid different from that containing at least one of the primary amine, secondary amine and tertiary amine.

6. A dry film, characterized in that, The dry film comprises a resin layer formed from the curable resin composition of claim 1.

7. A cured product, characterized in that, The cured product is obtained by curing the resin layer of the multi-component curable resin composition according to any one of claims 1 to 5 or the dry film according to claim 6.

8. An electronic component, characterized in that, The electronic component has the cured material as described in claim 7.

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