TW202026354A - Curable resin composition, dry film, cured product, printed circuit board, and electronic component - Google Patents

Abstract

Provided is a curable resin composition or the like having excellent high temperature exposure resistance and hardly generating any outgas when having a heat history of high temperature for an extended period of time on a package substrate, that is, being able to suppress decrease of weight, while satisfying performances necessary for solder resist, such as high adhesion, high resolution, high insulation reliability (HAST resistance), and high crack resistance (TCT resistance). This curable resin composition or the like contains a carboxyl group-containing resin (A), an epoxy resin (B), a photopolymerization initiator (C), and an inorganic filler (D), and is characterized in that the epoxy resin (B) has a Gardner color scale of less than or equal to 3, and that the epoxy resin (B) contains an epoxy resin (B-1) having the structure in formula (I), and a liquid trifunctional epoxy resin (B-2) having an isocyanuric ring.

Description

Curable resin composition, dry film, cured product, printed wiring board and electronic parts

The present invention relates to a curable resin composition, dry film, cured product, printed wiring board and electronic parts.

In recent years, with the rapid development of semiconductor components, electronic equipment is becoming more and more lighter, thinner, shorter, higher performance, and more versatile. In response to this trend, the miniaturization and pinning of semiconductor packages has been put into practical use. Specifically, in order to replace IC packages called QFP (Quad Flat Package), SOP (Small Outline Package), etc., IC packages called BGA (Ball Grid Array Package), CSP (Chip Scale Package), etc. are used. In addition, in recent years, FC-BGA (Flip Chip Ball Grid Array) has also been put into practical use as a higher density IC package. In the printed wiring boards (also called package substrates) used in this type of IC packaging, SROs (Solder Resist Openings) are formed close to each other due to the small pitch, which increases the possibility of short circuit or crosstalk noise between SROs. Furthermore, the solder mask formed between the SROs is prone to cracks due to getting thinner and thinner. Therefore, permanent coatings such as solder resists used in package substrates require long-term high reliability, specifically high insulation reliability. In particular, with the increasing density of package substrates in the future, it is believed that higher reliability is required. Prior art literature Patent literature

Patent Document 1: Japanese Patent No. 5167113

The problem to be solved by the invention

However, with regard to this reliability, the thermosetting resin composition described in Patent Document 1 has become insufficient in recent years. In addition, in recent years, in wire bonding and mounting package substrates, due to the increase in the number of I/Os or for the purpose of low cost, the wire material has been changed from gold to copper, and high temperature and long time heat is applied to the package substrate during wire bonding The specifications of the process have increased, and at this time, the generation of exhaust from the solder mask has become a problem. If the solder mask generates exhaust gas, it will contaminate the capillary tube, resulting in a shorter life span of the capillary tube, resulting in an increase in production costs or a deterioration in yield.

Therefore, the object of the present invention is to provide a solder resist layer that can meet the performance requirements of high adhesion, high resolution, high insulation reliability (HAST resistance), high crack resistance (TCT resistance), etc., and apply high temperature to the package substrate. The curable resin composition with excellent high-temperature storage resistance and the dry film having a resin layer obtained from the curable resin composition, the curable resin, produces less exhaust during the long-term thermal history, which can suppress weight loss The composition or the cured product of the resin layer of the dry film, the printed wiring board having the cured product, and the electronic component having the printed wiring board. Means to solve the problem

(B-2)具有異氰脲酸環之液狀3官能環氧樹脂。The inventors of the present case have worked hard to repeat the research and development for many times and found that through combined use, the Gardner color of the epoxy resin is 3 or less and the light transmittance is high, and as the epoxy resin, the skeleton contains triphenol methane and bisphenol The aforementioned epoxy resin of A, and the specific epoxy resin, can obtain a hardened product that generates less exhaust gas, and finally completed the present invention. That is, the curable resin composition of the present invention is a curable resin composition containing (A) a carboxyl group-containing resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) an inorganic filler It is characterized in that: (B) the Gardner color of epoxy resin is 3 or less, and (B) epoxy resin contains: (B-1) epoxy resin with the structure of the following formula (I), and

(B-2) Liquid trifunctional epoxy resin having isocyanuric acid ring.

In the curable resin composition of the present invention, the content of the aforementioned (D) inorganic filler is preferably 30 to 70% by mass, and the aforementioned (C) photopolymerization initiator is preferably an oxime ester; and the aforementioned (B-2) ) The liquid trifunctional epoxy resin having an isocyanuric acid ring is preferably an epoxy resin having the structure of the following formula (II).

The dry film of the present invention is characterized by having a resin layer obtained by coating and drying the curable resin composition described above. In addition, the cured product of the present invention is characterized by curing the aforementioned curable resin composition or the aforementioned dry film resin layer. In addition, the printed wiring board of the present invention is characterized by having the above-mentioned cured product. Furthermore, the electronic component of the present invention is characterized by having the above-mentioned printed wiring board. Effect of invention

According to the present invention, it is possible to obtain a performance that can meet the requirements of a solder resist layer such as high adhesion, high resolution, high insulation reliability (HAST resistance), high crack resistance (TCT resistance), etc., and apply high temperature to the package substrate. There is less exhaust during the thermal history of time, which can suppress weight loss. A curable resin composition with excellent high temperature storage resistance, a dry film having a resin layer obtained from the curable resin composition, and the curable resin composition Or the cured product of the resin layer of the dry film, the printed wiring board having the cured product, and the electronic component having the printed wiring board.

Form of invention

The curable resin composition of the present invention is a curable resin composition containing (A) a carboxyl group-containing resin, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) an inorganic filler; its characteristics It lies in: (B) the Gardner color of epoxy resin is 3 or less, and (B) epoxy resin contains: (B-1) epoxy resin having the structure of the aforementioned formula (I), and (B-2) ) Liquid trifunctional epoxy resin with isocyanuric acid ring.

The curable resin composition system of the present invention has the following characteristics: As mentioned above with regard to (B) epoxy resin, Gardner has a chromaticity of 3 or less, high light transmittance, and contains trisphenol methane as the epoxy resin. With bisphenol A (B-1) the epoxy resin with the structure of the aforementioned formula (I), and (B-2) the liquid trifunctional epoxy resin with the isocyanuric acid ring, thereby reducing the production Exhaust gas can suppress weight loss and has excellent high temperature storage resistance. Among the characteristics of the (B) epoxy resin of the curable resin composition of the present invention, since the Gardner chroma is as low as 3 or less, that is, the light transmittance is high, the light can reach the curable resin coated The deep part of the envelope of the composition. Therefore, the reactivity of the photoreactive functional group contained in the (A) carboxyl group-containing resin or the like can also be increased in the deep part by the transmitted light, and the cured product can be sufficiently hardened. Furthermore, since the skeleton described in the feature of (B) epoxy resin of the curable resin composition of the present invention contains trisphenol methane and bisphenol A, (B-1) epoxy having the structure of the aforementioned formula (I) The resin is an aromatic polyfunctional epoxy with a high softening point, so it has excellent toughness and heat resistance, and (B-2) a liquid tri-functional epoxy resin with an isocyanuric acid ring, which can complete the reaction or increase the crosslinking density The effect is excellent. Therefore, the curable resin composition of the present invention can improve the reactivity of the epoxy because the epoxy resins (B-1) and (B-2) are used in combination. As described above, in the present invention, by using the (B) epoxy resin having the aforementioned characteristics, the reactivity of the (A) carboxyl group-containing resin can also be improved in the deep part, and even the reactivity of the epoxy can be improved. Therefore, decomposition can also be suppressed during high-temperature thermal history, whereby the effective resin composition of the present invention generates less outgassing, can suppress weight loss, and is excellent in high-temperature storage resistance.

The components of the curable resin composition of the present invention will be described below. In addition, the term (meth)acrylate in this specification refers to the general term acrylate, methacrylate and their mixtures, and the same applies to other similar expressions.

[(A) Resin containing carboxyl group] As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable in terms of photocuring properties and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. When using only a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond, in order to make the composition photocurable, it is necessary to use a compound having multiple ethylenically unsaturated groups in the molecule described later, that is, a photoreactive monomer. body. Specific examples of the carboxyl group-containing resin include the following compounds (either oligomer or polymer may be used).

(1) Copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Resins containing carboxyl groups.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc. and carboxyl-containing diols such as dimethylol propionic acid and dimethylol butyric acid Compounds and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, phenolic hydroxyl groups and Carboxyl group-containing urethane resin obtained by polyaddition reaction of glycol compound such as alcoholic hydroxyl compound.

(3) Combining diisocyanate with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, (Meth)acrylate of bifunctional epoxy resin such as phenolic epoxy resin or its partial acid anhydride modified product, carboxyl group-containing photosensitive amine obtained by polyaddition reaction of carboxyl group-containing diol compound and glycol compound Carboxylate resin.

(4) In the synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added to perform A carboxyl group-containing photosensitive urethane resin obtained by terminal (meth)acrylation.

(5) In the synthesis of the resin of (2) or (3) above, a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to have one isocyanate group and one or more (former A compound of acryloyl group is a photosensitive urethane resin containing a carboxyl group obtained by terminal (meth)acrylation.

(6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or more multifunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.

(7) The hydroxyl group of the bifunctional (solid) epoxy resin is further epoxidized with epichlorohydrin and the polyfunctional epoxy resin is reacted with (meth)acrylic acid, and the resulting hydroxyl group is added with dibasic acid anhydride and the resulting carboxyl group-containing photosensitive性resin.

(8) The bifunctional propylene oxide resin is reacted with dicarboxylic acids such as adipic acid, phthalic acid and hexahydrophthalic acid, and phthalic anhydride and tetrahydrophthalic acid are added to the first hydroxyl group produced. Polyester resin containing carboxyl group obtained from dicarboxylic acid anhydride, hexahydrophthalic anhydride, etc.

(9) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as an epoxy compound having multiple epoxy groups in one molecule and p-hydroxyphenethyl alcohol, and (meth)acrylic acid The alcoholic hydroxyl group of the reaction product obtained by the reaction of monocarboxylic acid containing unsaturated groups, and the reaction of maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. The resulting resin contains carboxyl groups.

(10) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide and propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid to obtain A carboxyl group-containing photosensitive resin obtained by reacting the reaction product with a polybasic acid anhydride.

(11) The reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid to make A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (1) to (11). In addition, the term (meth)acrylate in this specification refers to the general term acrylate, methacrylate and their mixtures, and the same applies to other similar expressions.

(A) The resin containing a carboxyl group may not be limited to those listed above, and may be used alone or in combination of multiple types. Among them, resins containing carboxyl groups, such as the aforementioned resins (10) and (11) containing carboxyl groups, are synthesized using phenolic compounds as starting materials. The HAST test under high voltage, that is, B-HAST resistance or PCT resistance, is excellent. Can be suitable for use.

(A) The acid value of the carboxyl group-containing resin is preferably 20 to 200 mgKOH/g. (A) If the acid value of the carboxyl group-containing resin is 20 to 200 mgKOH/g, it is easy to form a pattern of the cured product. More preferably, it is 50~130mgKOH/g.

In addition, the weight average molecular weight of the (A) carboxyl group-containing resin varies with the resin skeleton, and it is generally preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. If the weight average molecular weight is 2,000 or more, the development resistance of the film in the exposed area can be improved, and the resolution is excellent. On the other hand, if the weight average molecular weight is 150,000 or less, the solubility of the unexposed part is good, the resolution is excellent, and storage stability can also be improved. The weight average molecular weight can be determined by gel permeation chromatography.

(A) The blending amount of the carboxyl group-containing resin is based on the total amount of the curable resin composition excluding the solvent, and is, for example, 5-50% by mass, preferably 10-40% by mass. By setting it to 5 mass% or more, preferably 10 mass% or more, the strength of the coating film can be improved. In addition, by setting it to 50% by mass or less, preferably 40% by mass or less, the viscosity is appropriate and the workability can be improved.

[(B) Epoxy] [(B-1) Epoxy resin having a structure of formula (I) containing trisphenol methane and bisphenol A in the skeleton] The curable resin composition of the present invention is contained in the epoxy resin of the aforementioned formula (I) structure containing trisphenol methane and bisphenol A in the skeleton, which can be, for example, TECHMORE (registered trademark) VG3101L manufactured by Mitsui Chemicals Co., Ltd. or Acquired NC-6300H manufactured by Nippon Kayaku Co., Ltd. TECHMORE VG3101L is a light yellow solid with a softening point of 60°C, Gardner color 3 or less, epoxy equivalent 210g/eq., total chlorine 1000ppm or less, and has high heat resistance, low water absorption, and low curing shrinkage.

[(B-2) Liquid trifunctional epoxy resin having isocyanuric acid ring] The curable resin composition of the present invention includes a liquid trifunctional epoxy resin having isocyanuric acid ring, which can be, for example, TEPIC-VL and TEPIC-FL manufactured by Nissan Chemical Co., Ltd. are obtained; among these, TEPIC-VL is better due to heat resistance or low curing shrinkage. TEPIC-VL is an epoxy resin with the structure of the following formula (II). It is a colorless transparent liquid with Gardner color below 1 and is viscous. It also has an epoxy equivalent as small as 135g/eq., perchlor 200ppm or less, high heat resistance, high light resistance, low water absorption and low curing shrinkage.

The curable resin composition of the present invention and the epoxy resins of (B-1) and (B-2) above meet the requirement of "the Gardner color of epoxy resin is 3 or less" of the present invention. The range that does not impair the unique effects of the present invention may include epoxy resins other than the epoxy resins of (B-1) and (B-2). Examples of epoxy resins other than the epoxy resins of (B-1) and (B-2) above include epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin Resin; thioether type epoxy resin; brominated epoxy resin; novolac type epoxy resin; bisphenol novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidol Amine type epoxy resin; Hydantoin type epoxy resin; Alicyclic epoxy resin; Trihydroxyphenylmethane type epoxy resin; Dixylenol type or diphenol type epoxy resin or a mixture of these; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetrahydroxyphenylethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl Xylene ethylene ethane resin; epoxy resin containing naphthyl group; epoxy resin with dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and methyl Copolymerized epoxy resin based on glycidyl acrylate; epoxy modified polybutadiene rubber derivative; CTBN modified epoxy resin, but not limited to these.

(B) The blending amount of the epoxy resin is, for example, 10 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 60 parts by mass relative to 100 parts by mass of the carboxyl-containing resin (A). (B) If the blending amount of the epoxy resin is 10 parts by mass or more, the crack resistance and insulation reliability can be further improved; if it is 100 parts by mass or less, the storage stability can be improved.

In addition, the (B-1) skeleton contains the blending amount of the epoxy resin having the structure of formula (I) of trisphenol methane and bisphenol A, and (B-2) the liquid trifunctional ring having an isocyanuric acid ring The ratio of the blending amount of the oxygen resin is preferably 1:6-6:1 on a mass basis, and particularly preferably 1:3-3:1. (B-1) The blending amount of the epoxy resin with the structure of formula (I) containing triphenolmethane and bisphenol A in the skeleton is relative to (B-2) the liquid trifunctional epoxy with isocyanuric acid ring If the blending ratio of the resin is 1:6 or more, the heat resistance can be improved; (B-1) The blending amount of the epoxy resin with the structure of formula (I) containing trisphenol methane and bisphenol A is relative If the ratio of the blending amount of the liquid trifunctional epoxy resin having an isocyanuric acid ring to (B-2) is 6:1 or less, the developability or laminating properties will be good. In addition, (B) epoxy resin 100 mass parts of (B-1) skeleton contains trisphenol methane and bisphenol A, the blending amount of epoxy resin having the structure of formula (I) and (B-2) The total blending amount of the liquid trifunctional epoxy resin having an isocyanuric acid ring is preferably 50-100 parts by mass, more preferably 80-100 parts by mass. (B-1) The blending amount of the epoxy resin with the structure of formula (I) containing trisphenol methane and bisphenol A and (B-2) the liquid trifunctional epoxy resin with isocyanuric acid ring If the total blending amount is 50 parts by mass or more, the effect of heat resistance and reduction of exhaust gas can be obtained.

[(C) Photopolymerization initiator] As the (C) photopolymerization initiator, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used. For example, bis-(2,6- Dichlorobenzyl) phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-2,5-dimethylphenyl phosphine oxide, bis-(2,6-dichlorobenzyl) (Amino)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzyl) )Phenyl phosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethylpentyl phosphine oxide, bis-(2,6-dimethoxybenzyl) (Amino)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzyl)phenylphosphine oxide (Omnirad 819 manufactured by IGM Resins), etc. Phosphine oxides; 2,6-dimethoxybenzyl diphenyl phosphine oxide, 2,6-dichlorobenzyl diphenyl phosphine oxide, 2,4,6-trimethylbenzyl Methyl phenyl phosphinate, 2-methyl benzyl diphenyl phosphinate, p-pentyl phenyl phosphinate isopropyl, 2,4,6-trimethyl benzyl two Phenyl phosphine oxide (Omnirad TPO manufactured by IGM Resins), etc.; mono-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanyl)benzyl]phenyl}-2- Hydroxyacetophenones such as methyl-propane-1-one and 2-hydroxy-2-methyl-1-phenylpropane-1-one; benzoin, biphenyl, benzoin Ether, benzoin ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether and other benzoins; benzoin alkyl ethers; benzophenone, p- Benzophenones such as methyl benzophenone, Michler's ketone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, etc. Class; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone, 2-benzyl-2-dimethylamino-1 -(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholine) Acetophenones such as phenyl)-1-butanone and N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone , 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2-chlorothioxanthone, 2,4-Diisopropylthioxanthone and other thioxanthones; Anthraquinone , Chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone, etc. Quinones; acetophenone dimethyl acetal, benzyl dimethyl Acetals such as acetals; ethyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, ethyl p-dimethylbenzoate and other benzoic acid esters; 1, 2-octanediol, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene (Formyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other oxime esters; bis(η5-2,4-cyclopentadien-1-yl)- Bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1 -Pyridin-1-yl)ethyl)phenyl)titanium and other titanocenes; phenyl disulfide 2-nitropyridine, butyroin, anisoin ethyl ether, azo Bisisobutyronitrile, tetramethylthiuram disulfide, etc. The photopolymerization initiator may be used alone or in combination of two or more kinds. Among them, monophosphine oxides and oxime esters are preferred, and 2,4,6-trimethylbenzyl diphenyl phosphine oxide, ethyl ketone, 1-[9-ethyl-6- (2-Methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime).

(C) The blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. If it is 0.5 parts by mass or more, the surface hardenability is good; if it is 20 parts by mass or less, halo is less likely to occur and good resolution can be obtained.

[(D) Inorganic filler] The curable resin composition of the present invention contains (D) an inorganic filler. The inorganic filler is not particularly limited. Well-known and customary fillers such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, and magnesium carbonate can be used. , Calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, slag wool, aluminosilicate, calcium silicate, zinc bloom and other inorganic fillers Agent. Among them, silicon dioxide is preferable, and spherical silicon dioxide is more preferable in terms of small surface area, stress can be dispersed to the whole and not easily become the starting point of cracks.

Inorganic fillers can be subjected to photoreactive surface treatment so that they have vinyl, styryl, methacrylic, acrylic, etc. as photocurable reactive groups; in this case, methacrylic is particularly preferred Acrylic, acrylic, vinyl. In addition, it can also be subjected to heat-reactive surface treatment to have hydroxyl, carboxyl, isocyanate, amino, imino, epoxy, oxetanyl, mercapto, and methyl groups as the thermosetting reactive groups. Oxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, oxazolinyl, etc.; in this case, particularly preferred are amino and epoxy groups. Furthermore, (D) inorganic filler may have 2 or more types of hardening reaction groups. (D) The inorganic filler is preferably surface-treated silica. By including surface-treated silicon dioxide, the CTE can be reduced and the glass transition temperature can be increased.

(D) The introduction method when introducing the hardenable reactive group into the surface of the inorganic filler is not particularly limited, as long as it is introduced by a well-known and customary method; as long as the surface treatment agent has a hardenable reactive group, for example, a hardenable reactive group The coupling agent can be used to treat the surface of the inorganic filler.

(D) The surface treatment of the inorganic filler is preferably a surface treatment using a coupling agent. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. can be used. Among them, a silane coupling agent is preferred.

The silane coupling agent is preferably a silane coupling agent capable of introducing a hardening reactive group to the (D) inorganic filler. Silane coupling agents that can introduce thermosetting reactive groups include epoxy-containing silane coupling agents, amine-containing silane coupling agents, mercapto-containing silane coupling agents, and isocyanate groups-containing silane coupling agents. Among them, silane coupling agents are more preferred. Silane coupling agent with epoxy group. As the silane coupling agent capable of introducing a photohardening reactive group, a silane coupling agent having a vinyl group, a silane coupling agent having a styrene group, a silane coupling agent having a methacryl group, and a silane having an acrylic group are preferred. The coupling agent is more preferably a silane coupling agent having a methacryl group.

When the (D) inorganic filler is surface-treated, it is only necessary to blend it with the curable resin composition of the present invention in a surface-treated state, and it is also possible to blend the untreated (D) inorganic filler and the surface separately The treatment agent is used for surface treatment of the (D) inorganic filler in the composition, but it is preferable to pre-mix the surface-treated (D) inorganic filler. By blending the (D) inorganic filler that has been surface-treated beforehand, it is possible to prevent the deterioration of crack resistance caused by the surface treatment agent that may remain without surface treatment and consumed during individual blending. When surface treatment is carried out in advance, it is preferable to blend a pre-dispersed liquid pre-dispersed with (D) inorganic filler into the solvent or resin component, and it is more preferable to pre-disperse the surface-treated (D) inorganic filler in the solvent, and The pre-dispersion liquid is blended into the composition, or the pre-dispersion liquid is blended into the composition after sufficient surface treatment is performed when the surface-untreated (D) inorganic filler is pre-dispersed in a solvent.

In the curable resin composition of the present invention, the (D) inorganic filler has an average particle size of 1 μm or less, and it is preferable that it is more excellent in crack resistance. More preferably, it is 0.8 μm or less. Furthermore, the present specification, the average particle size means the D ₅₀ value of, for example, using a value based Nikkiso Microtrac particle size analyzer manufactured measured.

In addition, (D) the inorganic filler has a maximum particle size of 4.0 μm or less, and it is preferable that it reacts efficiently and has better crack resistance and adhesion. More preferably, it is 3.0 μm or less. In addition, in this specification, the maximum particle size refers to the value of D ₁₀₀ , and is a value measured using, for example, a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.

The blending amount of the inorganic filler is preferably 30 to 80% by mass, more preferably 30 to 75% by mass, and still more preferably 35 to 70% by mass per unit of the total solid content of the curable resin composition.

(Compounds with ethylenically unsaturated bonds) The curable resin composition of the present invention may also contain a compound having an ethylenically unsaturated bond such as a photopolymerizable oligomer or a photopolymerizable vinyl monomer.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth)acrylate-based oligomers. Examples of (meth)acrylate oligomers include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol-type epoxy (meth)acrylic acid. Epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether ( Meth)acrylate, polybutadiene modified (meth)acrylate, etc.

As well-known and customary photopolymerizable vinyl monomers, for example, styrene derivatives such as styrene, chlorostyrene, α-methylstyrene, etc.; vinyl acetate, vinyl butyrate, or vinyl benzoate Vinyl esters such as vinyl isobutyl ether, vinyl n-butyl ether, vinyl tertiary butyl ether, vinyl n-pentyl ether, vinyl isopentyl ether, vinyl n-octadecyl ether Ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether and other vinyl ethers; acrylamide, methacrylamide, N-hydroxymethyl Of acrylamide, N-hydroxymethyl methacrylamide, N-methoxy methacrylamide, N-ethoxy methacrylamide, N-butoxy methacrylamide, etc. ( (Meth)acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, etc.; 2-ethyl (meth)acrylate Hexyl ester, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. (Meth) acrylic acid esters; (meth) hydroxy ethyl acrylate, (meth) hydroxy propyl acrylate, pentaerythritol tri (meth) acrylate and other hydroxyalkyl (meth) acrylates; (meth) ) Alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl acrylate, ethoxyethyl (meth)acrylate, etc.; ethylene glycol two (meth)acrylate, butanediol two (Meth) acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate and other alkylene polyol poly (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) Base) acrylic acid, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate and other polyoxyalkylene glycols poly(meth)acrylates; hydroxypivalate Poly(meth)acrylates such as pentanediol di(meth)acrylate; isocyanurate type poly((meth)acryloxyethyl]isocyanurate, etc. Meth) acrylates and the like. It can be used alone or in combination of two or more according to the required characteristics.

The blending amount of the compound having an ethylenically unsaturated bond is preferably 3 to 40 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. If it is 3 parts by mass or more, surface hardenability can be improved; if it is 40 parts by mass or less, halation can be suppressed. More preferably, it is 5-30 parts by mass.

(Thermal hardening catalyst) The curable resin composition of the present invention preferably contains a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4 -(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl Amine compounds such as amines, hydrazine compounds such as dihydrazine adipate and dihydrazine sebacate; phosphorus compounds such as triphenylphosphine, etc. Moreover, guanamine, acetguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2, 4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine‧isocyanuric acid adduct, 2,4-diamino-6-methacrylic acid S-triazine derivatives such as acetoxyethyl-S-triazine and isocyanuric acid adducts are preferably used in combination with these compounds that can also function as adhesion imparting agents and thermosetting catalysts.

The blending amount of the thermosetting catalyst is preferably 0.05 to 40 parts by mass, and more preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the epoxy resin (B).

(hardener) The curable resin composition of the present invention may contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. The curing agent can be used alone or in combination of two or more kinds.

The hardening agent is preferably based on the ratio of the functional group in the hardening agent that can react with the functional group in the hardening agent such as the epoxy group of the thermosetting resin such as epoxy resin and the like, and the functional group in the hardening agent. Functional group/functional group capable of thermal hardening reaction (equivalent ratio)=0.2~3 blended. By setting it in the above range, the balance between storage stability and curability is excellent.

(Colorant) The curable resin composition of the present invention may contain a colorant. As the coloring agent, known coloring agents such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments can be used. However, from the viewpoint of reducing the environmental load and the impact on the human body, it is preferable not to contain halogen.

The addition amount of the coloring agent is not particularly limited, and the ratio of preferably 10 parts by mass or less, particularly preferably 0.1-7 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin (A) is sufficient.

(Organic solvents) The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or carrier film. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone can be used; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbamide Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether and other glycols Ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ethyl Acid esters, dipropylene glycol monomethyl ether acetate, propylene carbonate and other esters; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, solvent naphtha and other petroleum-based solvents, etc. are well-known and commonly used The organic solvent. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

(Other optional ingredients) Furthermore, the curable resin composition of the present invention may also be blended with other additives commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, defoamers, leveling agents, and thickening agents. Agent, adhesion imparting agent, thixotropy imparting agent, photoinitiator, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stability Agent, phosphor, etc.

The curable resin composition of the present invention may contain thermosetting resins other than the (C) epoxy resin within a range that does not impair the effects of the present invention. As the thermosetting resin, any resin that can be cured by heating to exhibit electrical insulation, and examples thereof include (C) epoxy compounds other than epoxy resins, oxetane compounds, melamine resins, and poly Silicone resin, etc., can also be used together.

The curable resin composition of the present invention can be used as a dry film, or can be used in a liquid state. When used as a liquid, it can be one-component or two-component or more.

Next, the dry film of the present invention has a carrier film coated with the curable resin composition of the present invention and dried to obtain a resin layer. When forming a dry film, the curable resin composition of the present invention is first diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate viscosity, and then the cut-off wheel coater, knife coater, lip die coater, rod Coaters, rubber roll coaters, reverse roll coaters, conveyor roll coaters, gravure coaters, spray coaters, etc., coat the carrier film to a uniform thickness. Thereafter, by drying the coated composition at a temperature of generally 40 to 130°C for 1 to 30 minutes, a resin layer can be formed. The coating film thickness is not particularly limited, but it is generally calculated as the film thickness after drying, and is appropriately selected in the range of 3 to 150 μm, preferably 5 to 60 μm.

As the carrier film, a plastic film is used, such as polyester film such as polyethylene terephthalate (PET), polyimide film, polyimide film, polypropylene film, and polystyrene film. Wait. The thickness of the carrier film is not particularly limited, but it is generally selected appropriately within the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After the resin layer composed of the curable resin composition of the present invention is formed on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. The cover film should just be one that is smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In addition, in the present invention, a resin layer may be formed by coating the curable resin composition of the present invention on the above-mentioned cover film and drying, and laminating a carrier film on the surface thereof. That is, as a film for coating the curable resin composition of the present invention when a dry film is produced in the present invention, either a carrier film or a cover film can be used.

The printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or a resin layer of a dry film. As the manufacturing method of the printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and the substrate is coated by a dip coating method. , Flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc. After coating, the organic solvent contained in the composition is evaporated and dried at a temperature of 60~100℃ (Temporarily dry) to form a non-tacky resin layer. In the case of a dry film, the resin layer is bonded to the base material by a laminator or the like so that the resin layer is in contact with the base material, and then the carrier film is peeled off to form a resin layer on the base material.

As the above-mentioned substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed with copper in advance, the use of paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass Cloth/non-woven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin, polyethylene, polyphenylene oxide, polyphenoxide, cyanate ester, etc. Copper-clad laminates for high frequency circuits, etc. The materials of all grades (FR-4, etc.) are copper-clad laminates, as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, crystals Round plates and so on.

The volatilization drying performed after coating the curable resin composition of the present invention can use a hot air circulation type drying furnace, IR furnace, hot plate, convection oven, etc. (using a heat source equipped with an air heating method by steam to make the inside of the dryer The method of hot air convection contact and the method of spraying the support by the nozzle).

After the resin layer is formed on the printed wiring board, it is selectively exposed with active energy rays through a mask formed with a predetermined pattern, and the unexposed area is developed by a dilute alkali aqueous solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution), And form the pattern of the hardened object. Furthermore, the cured product is irradiated with active energy rays and then heated and cured (for example, 100 to 220°C) or heated and cured after being irradiated with active energy rays, or only heated and cured, and the curing is finally completed (full curing), and various properties such as adhesion and hardness are formed. Excellent hardened film. In addition, when the curable resin composition of the present invention contains a photobase generator, it is preferably heated after exposure and before development; as the heating condition after exposure and before development, it is preferable to heat, for example, 60 to 150°C for 1~ 60 minutes.

As the exposure machine used for the above-mentioned active energy ray irradiation, as long as it is equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm, direct drawing can also be used. Device (for example, a direct laser imaging device that uses CAD data from a computer to draw an image directly with a laser). As the light source or laser light source of the direct drawing machine, the maximum wavelength should be in the range of 350~450nm. The amount of exposure used for image formation varies with the thickness of the film, but generally it can be 10~1000mJ/cm ² , preferably in the range of 20~800mJ/cm ² .

As the above-mentioned developing method, immersion method, leaching method, spray method, brushing method, etc. can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicic acid can be used. Alkaline aqueous solutions such as sodium, ammonia, amines, etc.

The curable resin composition of the present invention is suitable for forming a cured film on a printed wiring board, more suitable for forming a permanent film, and even more suitable for forming a solder resist layer, an interlayer insulating layer, and a cover film. In addition, the curable resin composition according to the present invention can obtain a cured product with excellent crack resistance and insulation reliability, and is suitable for printed wiring boards with fine-pitch wiring patterns that require high reliability, such as package substrates. Especially for the formation of permanent film (especially solder mask) for FC-BGA. Example

The following examples illustrate the present invention in more detail, but the present invention is not limited by the following examples. In addition, the following "parts" and "%", unless otherwise specified, are all quality standards.

[(A)-1 Synthesis of carboxyl group-containing resin] Into an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, a novolak type cresol resin (SHONOL CRG951, OH manufactured by Showa Denko) Equivalent: 119.4) 119.4 parts, 1.19 parts of potassium hydroxide, and 119.4 parts of toluene, replace nitrogen in the system while stirring, and heat up. Secondly, 63.8 parts of propylene oxide was slowly added dropwise, and reacted at 125-132°C and 0-4.8 kg/cm ² for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added and mixed in the reaction solution to neutralize potassium hydroxide to obtain a novolac with 62.1% non-volatile content and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.) Propylene oxide reaction solution of type cresol resin. The phenolic hydroxyl group has an average addition of 1.08 mol per 1 equivalent of propylene oxide. Introduce 293.0 parts of the propylene oxide reaction solution of the novolak type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methyl hydroquinone, and 252.9 parts of toluene into a reactor equipped with a mixer, a thermometer and an air blowing tube Blow in air at a rate of 10ml/min, and react at 110°C for 12 hours while stirring. The water produced by the reaction is used as an azeotropic mixture with toluene, distilling 12.6 parts of water. After cooling to room temperature, the resulting reaction solution was neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, and then washed with water. Subsequently, the toluene was replaced with 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolac type acrylate resin solution. Next, introduce 332.5 parts of the obtained novolac-type acrylate resin solution and 1.22 parts of triphenylphosphine into a reactor equipped with a stirrer, a thermometer and an air blowing tube, blow in air at a rate of 10ml/min, and slowly add while stirring 60.8 parts of tetrahydrophthalic anhydride, react at 95~101°C for 6 hours, take it out after cooling. In this way, a photosensitive (A)-1 carboxyl group-containing resin solution with a solid content of 65% and an acid value of the solid content of 87.7 mgKOH/g was obtained. Hereinafter, the solution of the photosensitive resin containing the carboxyl group is referred to as (A)-1 resin solution.

[(A)-2 Synthesis of carboxyl-containing resin] 600 g of diethylene glycol monoethyl ether acetate was fed with o-cresol novolac type epoxy resin (EPICLON N-695 manufactured by DIC Corporation, softening point 95°C, epoxy equivalent 214, average functional group number 7.6) 1070 g (epoxy Propyl number (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone, heated to 100°C and stirred to uniformly dissolve. Next, 4.3 g of triphenylphosphine was fed, and after heating to 110° C. for reaction for 2 hours, the temperature was raised to 120° C. for further reaction for 12 hours. The obtained reaction liquid was fed with 415 g of aromatic hydrocarbon (SOLVESSO 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride, and the reaction was carried out at 110°C for 4 hours and cooled to obtain photosensitive (A)- 2 Resin solution containing carboxyl group. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 89 mgKOH/g. Hereinafter, this solution of the photosensitive resin containing a carboxyl group is referred to as resin solution (A)-2.

[(A)-3 Synthesis of carboxyl-containing resin] In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux cooler, heat 325.0 parts of dipropylene glycol monomethyl ether as a solvent to 110°C, and add 174.0 parts of methacrylic acid and ε-caprolactone dropwise over 3 hours. 174.0 parts of methacrylic acid (average molecular weight 314), 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and tertiary butylperoxy 2-ethylhexanoate (NOF Corporation) as a polymerization catalyst A mixture of 12.0 parts of PERBUTYL O) was prepared and further stirred at 110°C for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After cooling the resin solution, 289.0 parts of Cyclomer A200 manufactured by DAICEL Chemical Industry Co., Ltd., 3.0 parts of triphenylphosphine, and 1.3 parts of hydroquinone monomethyl ether were added. The temperature was raised to 100°C and stirred to carry out ring-opening addition of epoxy groups. It reacts to obtain a photosensitive resin solution containing carboxyl groups. The weight average molecular weight (Mw) of the resin solution thus obtained was 15,000, the solid content was 57%, and the acid value of the solid matter was 79.8 mgKOH/g. Hereinafter, the solution of the photosensitive resin containing this carboxyl group is referred to as resin solution (A)-3.

(Examples 1 to 17 and Comparative Examples 1 to 3) For the above synthesized (A)-1~3 carboxyl-containing resin (up to 100 parts by mass), the ingredients shown in Tables 1 to 3 are blended in the proportions shown in Tables 1 to 3, according to each example and comparative example Using a die coater, the curable resin composition was passed through a drying oven at 60 to 120° C. on PET at 10 m/min to volatilize the solvent to obtain a dry film. In addition, the blending amounts in Tables 1 to 3 are all solids conversion values. The obtained dry film was laminated on a test substrate using a vacuum laminator CVP-300 (manufactured by Nikko-Materials) to obtain laminates of the curable resin compositions of Examples 1 to 17 and Comparative Examples 1 to 3. Here, since the test substrate and the lamination method vary with the evaluation items, it is recorded in one of the evaluation items below. In order to use DXP-3580 (manufactured by ORC, ultra-high pressure mercury lamp DI exposure machine) on this laminate, a Stouffer 41 layer exposure grid number table was used to form 10 hardened layers, and pattern exposure was carried out according to the evaluation items. Regarding the other exposure conditions, since it varies with each evaluation item, it is recorded in one of the following evaluation items. After 10 minutes of exposure, the PET film was peeled off and developed with a 1% by mass aqueous sodium carbonate solution at 30°C with a development time twice the development point (shortest development time). After that, exposure was carried out at 2000mJ using a UV conveyor (manufactured by ORC, metal halide lamp), and cured at 170°C for 60 minutes using a thermal cycle box furnace to obtain Examples 1 to 17 and Comparative Example 1. ~3 evaluation substrate of curable resin composition. In addition, the development and curing conditions described in this paragraph are used for development, and those who are cured are described in one of the following evaluation items as "development and curing under the predetermined conditions".

For the evaluation substrates of the curable resin compositions of Examples 1 to 17 and Comparative Examples 1 to 3 prepared in this way, Tg, thermal weight reduction, exhaust, curing inhibition by thermal history, adhesion, analysis, and HAST were performed Evaluation of tolerance and TCT tolerance. These evaluation results are shown in Tables 1 to 3.

(Glass transition temperature Tg evaluation) Each curable resin composition was formed on a copper foil substrate with a film thickness of approximately 40 μm, and exposed in a strip pattern of 50 mm×3 mm. After that, development and curing are carried out under predetermined conditions. The cured film of the evaluation substrate obtained above was peeled from the copper foil, and the evaluation was performed for Tg. The measurement system used a TMA measurement device (model name: TMA6000 manufactured by Shimadzu Corporation). The evaluation criteria are as follows. ◎: 180°C or higher. ○: 170°C or higher and less than 180°C. △: 160°C or higher and less than 170°C. ×: It has not reached 160°C.

(Evaluation of thermal weight reduction) On a copper-plated substrate treated with CZ-8101B at an etching rate of 1.0 μm/m ² , a curable resin composition was formed with a film thickness of about 15 μm, and the entire surface was exposed. After that, development and curing are carried out under predetermined conditions. Approximately 5 mg of the cured film powder sample of the obtained evaluation substrate was taken and heated at 140°C for 90 minutes with a TGDTA device manufactured by Rigaku Corporation, and the weight loss rate after reaching 140°C was evaluated. The evaluation criteria are as follows. ◎: Less than 0.025%. ○: 0.025% or more and less than 0.050%. △: 0.050% or more and less than 0.075%. ×: 0.075% or more.

(Emission evaluation) On a copper-plated substrate treated with CZ-8101B at an etching rate of 1.0 μm/m ² , a curable resin composition was formed with a film thickness of approximately 15 μm, and the entire surface was exposed. After that, development and curing are carried out under predetermined conditions. About 1 mg of the hardened coating powder sample of the obtained evaluation substrate was taken and heated under the following thermal extraction conditions. After condensing and trapping volatile components, it is quickly heated and introduced into GC/MS for evaluation. Using the following evaluation device, the extraction conditions and evaluation criteria are as follows. (1) Evaluation device Heating desorption device: Gerstel Co., Ltd. product TDU GC: Agilent Technologies Co., Ltd. product 6890N MSD: Agilent Technologies Co., Ltd. product 5973N (2) Extraction conditions Hot extraction conditions: 220°C for 10 minutes. (3) Evaluation criteria ◎: Less than 0.020%. ○: 0.020% or more and less than 0.040%. △: 0.040% or more and less than 0.060%. ×: 0.060% or more.

(Evaluation of inhibition of hardening by thermal history) Each curable resin composition was formed on a copper foil substrate with a film thickness of approximately 40 μm, and exposed in a strip pattern of 50 mm×5 mm. After that, development and curing are carried out under predetermined conditions. The cured film of the evaluation substrate obtained above was peeled off from the copper foil, and the Tg was measured using DMA (RSA-G2 manufactured by TA) and the result was set as (1); and the evaluation substrate obtained above was again evaluated as 150 After curing under the condition of ℃ for 24 hours, the cured film of the substrate was evaluated by peeling off the copper foil in the same way. Tg was measured using DMA (RSA-G2 manufactured by TA) and the result was set as (2), according to (1) The value difference with (2) is evaluated. The evaluation criteria are as follows. ◎: It is less than 15°C. ○: 15°C or more and less than 30°C. △: 30°C or higher and less than 45°C. ×: 45°C or higher.

(Evaluation of Adhesion) A curable resin composition was formed on the copper foil treated with CZ-8201B under the condition of an etching rate of 0.5 μm/m ² to have a film thickness of about 20 μm, and the entire surface was exposed. After that, development and curing are carried out under predetermined conditions. After that, the thermosetting adhesive Araldite (manufactured by NICHIBAN) was formed on the surface of the curable resin composition, and it was adhered to the FR-4 substrate and cured under the conditions of 80°C for 6 hours. After that, the evaluation substrate was cut at an interval of 20 mm, and both sides were peeled off so that the width of the Cu foil was 10 mm in width, to prepare a strip for evaluation. The strips for evaluation were subjected to a 90° peel test using a tensile tester (manufactured by Shimadzu Corporation, model name: AGS-G 100N) to evaluate the adhesion. The evaluation criteria are as follows. ◎: 6.0 N/cm or more. ○: 5.0 or more and less than 6.0 N/cm. △: 4.0 or more and less than 5.0 N/cm. ×: Less than 4.0 N/cm.

(Analytical evaluation) On a copper-plated substrate treated with CZ-8101B at an etching rate of 1.0μm/m ² , a curable resin composition is formed with a film thickness of about 15μm, and is performed with various opening patterns exposure. After that, curing is carried out in accordance with the development and evaluation conditions under the established conditions. Observe the aperture diameter of the evaluation substrate obtained above to confirm that there is no halation or undercut generation for evaluation. The evaluation criteria are as follows. ⊚: It is a good opening diameter of 60 μm. ○: It is a good aperture diameter of 70 μm. △: 80 μm, which is a good opening diameter. ×: It is 80 μm and a good aperture diameter cannot be obtained; or the image cannot be developed.

(Evaluation of resistance to the HAST) is formed in the treatment of conditions CZ-8101B by etch rate 1.0μm / m ² has the L / S = a 20 / 15μm of a comb pattern on the substrate to a thickness of about 15 m Cu manner The curable resin composition is formed, and the entire surface is exposed. After that, development and curing are carried out under predetermined conditions. After that, the electrodes were connected and the HAST test was performed at 130°C, 85%, and 5V. The evaluation criteria are as follows. ◎: Passed for 400 hours. ○: Passed for 350 hours. △: Passed for 300 hours. ×: NG within 250 hours.

(TCT resistance) on the package substrate to be processed according to conditions CZ-8101B etch rate of 1.0μm / m ^2, the film thickness of about 15μm of Cu is formed of curable resin composition, and exposed to a copper pad SRO80μm . After that, development and curing are carried out under predetermined conditions. After that, gold plating is performed to form solder bumps and mount Si wafers to obtain a qualified substrate. The evaluation substrate obtained according to the above is placed in a thermal cycler that performs a temperature cycle between -65°C and 150°C, and performs TCT (Thermal Cycle Test). Then, observe the surface of the cured film at 600 cycles, 800 cycles, and 1000 cycles. The criterion is as follows. ◎: There is no abnormality in 1000 cycles. ○: No abnormality in 800 cycles. Cracks are generated in 1000 cycles. △: No abnormality in 600 cycles. Cracks are generated in 800 cycles. ×: Cracks were generated at 600 cycles.

The components used in the Examples and Comparative Examples described in Tables 1 to 3 are as follows. (*1): The aforementioned (A)-1 carboxyl-containing resin (carboxylic acid equivalent 640) (*2): The aforementioned (A)-2 carboxyl-containing resin (carboxylic acid equivalent 630) (*3) : The aforementioned (A)-3 carboxyl-containing resin (carboxylic acid equivalent 703) (*4): TECHMOREVG3101L manufactured by Mitsui Chemicals Co., Ltd. (epoxy resin with the structure of the aforementioned formula (I), epoxy equivalent 210, Gardner color 2) (*5): NC-6300H manufactured by Nippon Kayaku Co., Ltd. (epoxy resin with the structure of the aforementioned formula (I), epoxy equivalent 232, Gardner color 2) (* 6): TEPIC-VL manufactured by Nissan Chemical Co., Ltd. (liquid trifunctional epoxy resin with isocyanuric acid ring, epoxy equivalent 135, Gardner color 1) (*7): Nissan Chemical Co., Ltd. TEPIC-FL (liquid trifunctional epoxy resin with isocyanuric acid ring, epoxy equivalent 170, Gardner color 1) (*8): NC-7000L (multifunctional) manufactured by Nippon Kayaku Co., Ltd. Epoxy resin, containing aromatic (naphthalene) skeleton, epoxy equivalent 230, Gardner color> 12) (*9): DIC (stock) N-730-A (2.5 functional epoxy resin, containing aromatic (Phenolic novolac type) skeleton, epoxy equivalent 176, Gardner color 1) (*10): HP-4032 (two-functional epoxy resin, containing aromatic (naphthalene) skeleton, epoxy) made by DIC (Stock) Equivalent 142, Gardner color> 12) (*11): Omnirad TPO (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) manufactured by IGM Resins (*12): IGM Omnirad907 (2-methyl-1-(4-methylthienyl)-2-morpholinylpropan-1-one) manufactured by Resins (*13): IRGACURE OXE02 manufactured by BASF Japan (Ethyl Ketone, 1 -[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(o-acetoxime) (*14): Japan Institute of Chemical Industry ) TOE-04-A3 (oxime ester type) (*15): A silica dispersion product obtained according to the following manufacturing method. Spherical silica particles (Denka (Stock) SFP-20M, average particle size: 400nm) 50g, PMA48g as a solvent and 2g dispersant (BYK-111) are uniformly dispersed. (*16): Barium sulfate dispersion obtained according to the following manufacturing method. Barium sulfate particles (manufactured by Sakai Chemical Industry Co., Ltd.) Settling barium 100) After the 50g water slurry is heated to 70°C, a 10% sodium silicate aqueous solution of 1% based on silica particles is added to the silica particles. Hydrochloric acid is added to the slurry to adjust the pH to 4 , Aging for 30 minutes, and while maintaining the pH at 7 ± 1 with hydrochloric acid, adding ₂ to 5% of the silica particles in terms of alumina (Al ₂ O ₃ ) 0% sodium aluminate (NaAlO ₂ ) aqueous solution. After that, a 20% sodium hydroxide water bath was added to adjust the pH to 7, and aging was performed for 30 minutes. After that, the slurry was filtered and washed with water using a filter press and vacuum-dried to obtain a solid substance of barium sulfate particles coated with a hydrous oxide of silicon and a hydrous oxide of aluminum. It is formed by uniformly dispersing 50 g of barium sulfate particles coated with a hydrous oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111). (*17): Alumina dispersion obtained according to the following manufacturing method. It is formed by uniformly dispersing 50 g of spherical alumina particles (ASFP-20 manufactured by Denka Co., Ltd., average particle diameter: 300 nm), 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111). (*18): Dispersed silica obtained by the following manufacturing method. 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm), 48 g of PMA as a solvent, and a silane coupling agent having a methacrylic acid group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 2g is evenly dispersed. (*19): Dispersed silica obtained by the following manufacturing method. After heating a 50g water slurry of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400nm) to 70°C, add 1% of silica particles to silica particles. 10% sodium silicate aqueous solution. The slurry was added with hydrochloric acid to adjust the pH to 4 and matured for 30 minutes. Then, while maintaining the pH at 7±1 with hydrochloric acid, the slurry was added with respect to silica particles and converted to 5 by alumina (Al ₂ O ₃ ) % Of 20% sodium aluminate (NaAlO ₂ ) aqueous solution. After that, a 20% sodium hydroxide water bath was added to adjust the pH to 7, and aging was performed for 30 minutes. After that, the slurry was filtered and washed with a filter press and dried in a vacuum to obtain a solid material of silicon dioxide particles coated with a hydrous oxide of silicon and a hydrous oxide of aluminum. Mix 50 g of silica particles coated with a hydrous oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a methacrylic silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) Scattered. (*20): DPHA (Dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. (*21): Phthalocyanine Blue (*22): Cromophtal Yellow (*23): Melamine (*24): DICY (Dicyanide Diamine)

It can be seen from the results shown in Tables 1 to 3 that according to the curable resin composition of the present invention, it is possible to obtain high adhesiveness, high resolution, high insulation reliability (HAST resistance), and high crack resistance (TCT resistance). The performance required by the solder resist layer is required, and when a high temperature and long-term thermal history is applied to the package substrate, there is less outgassing, which can suppress weight loss. The resin layer obtained by a curable resin composition with excellent high temperature resistance Hardened object.

Claims (8)

A curable resin composition comprising: (A) a resin containing a carboxyl group, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) an inorganic filler; characterized by: (B) ring The Gardner color of the oxygen resin is 3 or less, and the (B) epoxy resin contains: (B-1) an epoxy resin having the structure of the following formula (I), and

(B-2) Liquid trifunctional epoxy resin having isocyanuric acid ring. The curable resin composition of claim 1, wherein the content of the aforementioned (D) inorganic filler is 30 to 70% by mass. The curable resin composition of claim 1, wherein the aforementioned (C) photopolymerization initiator is an oxime ester. The curable resin composition of claim 1, wherein the aforementioned (B-2) liquid trifunctional epoxy resin having an isocyanuric acid ring is an epoxy resin having a structure of the following formula (II),

. A dry film characterized by having a resin layer obtained by coating and drying the curable resin composition of claim 1 on a film. A cured product characterized by curing the curable resin composition of any one of claims 1 to 4 or the resin layer of the dry film of claim 5. A printed wiring board characterized by having a cured product as claimed in claim 6. An electronic component characterized by having a printed wiring board as in Claim 7.