TW202216797A - Curable resin composition and solder resist film formed therefrom, interlayer insulating material, and printed circuit board - Google Patents

Abstract

A curable resin composition and a solder resist film formed therefrom, an interlayer insulating material, and a printed circuit board. The curable resin composition comprises a photopolymerization initiator (A), a carboxyl-containing resin (B), and a photopolymerizable monomer (C). The photopolymerization initiator (A) comprises a first photopolymerization initiator (A1) and a second photopolymerization initiator (A2). The first photopolymerization initiator (A1) is one or more selected from a group consisting of a free-radical oxime ester-based photopolymerization initiator, a free-radical imidazole-based photopolymerization initiator, a alkyl phenyl ketone-based photopolymerization initiator, and an acyl phosphine oxide-based photopolymerization initiator, and the second photopolymerization initiator (A2) has a structure represented by general formula (I). The curable resin composition has excellent curability both in thick coatings and in systems having higher colorant content, and also has high resolution and better heat resistance, chemical resistance, and adhesion resistance.

Description

Curable resin composition, solder resist film, interlayer insulating material, and print formed therefrom Brush the circuit board

The present invention relates to the field of photocuring, in particular, to a curable resin composition, a solder resist film, an interlayer insulating material and a printed circuit board formed therefrom.

The printed wiring board has a conductor circuit pattern formed on a base material, electronic components are mounted on the pad portion of the conductor circuit by soldering, and the circuit portion other than the pad portion is covered with a solder resist to protect the conductor. The solder resist film used in the manufacturing process of the printed circuit board can not only protect the unrelated wiring during the soldering process, but also can be used as a plating protective layer during the plating process. Therefore, the solder resist film needs to have advantages such as heat resistance during soldering, chemical resistance during plating treatment, and insulation reliability after soldering. In addition, solder mask also reduces the risk of poor appearance of copper circuits due to heat, moisture or electricity, damage, dirt, etc. At the same time, in order to solve the above-mentioned problems, a colorant is usually added to the solder resist film and its concentration is increased, so that it is difficult for the user to see the defects in appearance. However, with the increase of the colorant concentration, the disadvantageous problem is that the curing is insufficient and the bottom drying is difficult.

On the other hand, in order to reduce power consumption and running cost, UV-LED lamps are usually used as curing light sources instead of conventional UV lamps. However, since UV-LED light has a long wavelength, the curing performance is low, and the curable resin composition cannot be cured sufficiently compared with the conventional UV lamps, which requires further improvement of the curability of the curable resin composition. At the same time, due to the copper circuit formed on the substrate, the resistance to In the case of a flux or a laminated solder resist, the thickness distribution of the resist film is thicker on the base material, thinner on the copper circuit, and thinner at the edge of the copper circuit. In the face of the above-mentioned situation of different thicknesses of the solder mask, when curing with a UV-LED light source, the defect that cannot be fully cured will become more obvious.

The main purpose of the present invention is to provide a curable resin composition, a solder resist film, an interlayer insulating material and a printed circuit board formed therefrom, so as to solve the problem that the existing curable composition cannot be sufficiently cured under a UV-LED light source.

In order to achieve the above object, one aspect of the present invention provides a curable resin composition, the curable resin composition comprising a photopolymerization initiator (A), a carboxyl group-containing resin (B) and a photopolymerizable monomer (C), and the photopolymerization The initiator (A) includes a first photopolymerization initiator (A1) and a second photopolymerization initiator (A2), wherein the first photopolymerization initiator (A1) is selected from the group consisting of free-radical oxime ester-based photopolymerization initiators, One or more of the group consisting of a radical-type imidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator, and the second photopolymerization initiator (A2) has The structure shown in general formula (I):

In formula (I), A represents hydrogen, nitro, halogen or -CO-CR ₂ R ₃ R ₄ group; two R ₁ are each independently selected from hydrogen, C ₁ ～C ₁₀ straight-chain alkyl or C ₃ -C ₁₀ branched-chain alkyl, or C ₂ -C ₁₀ alkenyl, or two R ₁ form a cyclic structure; R ₂ and R ₃ independently represent C ₁ -C ₁₀ straight-chain alkyl groups Or branched chain alkyl of C ₃ ~C ₁₀ ; R ₄ represents a photoactive group.

Further, in formula (I), two R ₁ are each independently selected from hydrogen, C ₁ -C ₆ straight-chain alkyl or C ₃ -C ₆ branched-chain alkyl or C ₂ -C ₆ alkene group, or two R ₁ form a four-, five- or six-membered ring.

Further, in formula (I), R ₂ and R ₃ independently represent a C ₁ -C ₆ straight-chain alkyl group or a C ₃ -C ₆ branched-chain alkyl group.

Further, in formula (I), R ₄ is hydroxyl or N-morpholinyl.

Further, A is hydrogen or a -CO-CR ₂ R ₃ R ₄ group, and R ₂ , R ₃ and R ₄ in the substituent -CO-CR ₂ R ₃ R ₄ group have the same definitions as described above .

Further, the weight ratio of the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) is (0.5~5):(5~9.5).

Further, the curable resin composition further includes a thermosetting component (D), preferably, the thermosetting component (D) is selected from blocked isocyanate compounds, amino resins, maleimide compounds, and benzoxazine resins , one or more of the group consisting of carbodiimide resins, cyclic carbonate compounds, multifunctional epoxy compounds, multifunctional oxetane compounds and episulfide resins.

Another aspect of the present application also provides a solder mask, which is formed by curing the curable resin composition provided by the present application.

Yet another aspect of the present application also provides a printed circuit board, including a solder mask, and the solder mask includes the above-mentioned solder mask.

Another aspect of the present application also provides an interlayer insulating material, which is formed by curing the above curable resin composition.

Apply the technical scheme of the present invention, adopt the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) to have better photoinitiating activity and stability, and use them as the photopolymerization initiator (A) The carboxyl group-containing resin (B) and the photopolymerizable monomer (C) can be cured more deeply, which is advantageous in improving the heat resistance and adhesiveness of the cured product formed therefrom. The carboxyl group-containing resin (B) enables the curable resin composition to be an alkali-developable curable resin composition, and improves the resolution of the developed pattern. The addition of the photopolymerizable monomer (C) can adjust the chemical resistance and curing rate of the above-mentioned curable composition. On this basis, the above compositions have excellent curability in both thick coatings and systems with high colorant content, as well as high resolution and good heat resistance, chemical resistance and adhesion. sex.

It should be noted that the embodiments in the present application and the features of the embodiments may be combined with each other in the case of no conflict. The present invention will be described in detail below with reference to the embodiments.

As described in the background art, the existing curable compositions cannot be sufficiently cured under UV-LED light sources. In order to solve the above technical problems, the present application provides a curable resin composition, the curable resin composition comprising a photopolymerization initiator (A), a carboxyl group-containing resin (B) and a photopolymerizable monomer (C), the photopolymerization initiator The agent (A) includes a first photopolymerization initiator (A1) and a second photopolymerization initiator (A2), wherein the first photopolymerization initiator (A1) is selected from free radical oxime ester-based photopolymerization initiators, free radicals One or more of the group consisting of a radical-type imidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator, and the second photopolymerization initiator (A2) has the following properties: The structure shown by general formula (I):

In formula (I), A represents hydrogen, nitro, halogen or -CO-CR ₂ R ₃ R ₄ group; two R ₁ are each independently selected from hydrogen, C ₁ ～C ₁₀ straight-chain alkyl or C ₃ -C ₁₀ branched-chain alkyl, C ₂ -C ₁₀ alkenyl, or two R ₁ form a cyclic structure; R ₂ and R ₃ independently represent C ₁ -C ₁₀ straight-chain alkyl or C ₃ ~C ₁₀ branched chain alkyl; R ₄ represents a photoactive group.

Using the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) has better photoinitiating activity and stability, and using them as the photopolymerization initiator (A) can interact with the carboxyl-containing resin (B) and The photopolymerizable monomer (C) is more deeply cured, and further contributes to improving the heat resistance and the adhesiveness of the cured product formed by the photopolymerizable monomer (C). The carboxyl group-containing resin (B) enables the curable resin composition to be an alkali-developable curable resin composition, and improves the resolution of the developed pattern. The addition of the photopolymerizable monomer (C) can adjust the chemical resistance and curing rate of the above-mentioned curable composition. On this basis, the above compositions have excellent curability in both thick coatings and systems with high colorant content, as well as high resolution and good heat resistance, chemical resistance and adhesion. sex.

Photopolymerization Initiator (A)

The photopolymerization initiator (A) specified as the aforementioned combination, wherein the photopolymerization initiator (A) includes a first photopolymerization initiator (A1) and a second photopolymerization initiator (A2), and the first photopolymerization initiator ( A1) Contains: a radical-type imidazole-based photopolymerization initiator, a radical-type oxime ester-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator. One or more, the second photopolymerization initiator (A2) has the structure shown in general formula (I):

In formula (I), A represents hydrogen, nitro, halogen or -CO-CR ₂ R ₃ R ₄ group; two R ₁ independently represent hydrogen, C ₁ -C ₁₀ straight-chain alkyl or C ₃ ~C ₁₀ branched alkyl or C ₂ -C ₁₀ alkenyl, or two R ₁ can also be connected to form a ring; R ₂ and R ₃ independently represent C ₁ -C ₁₀ straight chain alkyl or C ₃ ~C ₁₀ branched chain alkyl; R ₄ represents a photoactive group.

In a preferred embodiment, in formula (I), two R ₁ are each independently selected from hydrogen, C ₁ -C ₆ straight-chain alkyl or C ₃ -C ₆ branched-chain alkyl or C ₂ ~ _C6 alkenyl, or two R1 to form _a four-, five- or six-membered ring.

In a preferred embodiment, in formula (I), R ₂ and R ₃ independently represent a C ₁ -C ₆ straight-chain alkyl group or a C ₃ -C ₆ branched-chain alkyl group.

In a preferred embodiment, in formula (I), R ₄ is hydroxyl or N-morpholinyl.

In a preferred embodiment, A is hydrogen or a -CO-CR ₂ R ₃ R ₄ group, and R ₂ , R ₃ and R ₄ in the substituent -CO-CR ₂ R ₃ R ₄ group are the same as those described above. Corresponding parts have the same definitions.

Examples of halogen may include fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine.

Examples of the C ₁ -C ₁₀ straight-chain alkyl group may include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

Examples of the C ₃ -C ₁₀ branched chain alkyl group may include isopropyl, isobutyl, tert-butyl, isopentyl, tert-amyl, isohexyl, and the like.

Examples of the C ₃ -C ₁₀ cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

Examples of the C ₂ -C ₁₀ alkenyl group may include vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl and the like.

Examples of the four-membered, five-membered or six-membered ring formed by two R ₁ may include a cyclobutanyl ring, a cyclopentyl ring, and a cyclohexyl ring.

In a preferred embodiment, the radical type imidazole-based photopolymerization initiator is a bisimidazole-based photoinitiator; more preferably, the above-mentioned bisimidazole-based photoinitiator includes but is not limited to 2,2'-bis(o-chloro) Phenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) -4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tris(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)- 4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2 '-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2, 2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-methoxyphenyl)-4,4', 5,5'-Tetraphenyl-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4,4'-bis(3,4-dimethoxyphenyl)- 5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)- 5-(o-Chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4- Dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl) )-2',5-bis(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl) -4,4',5,5'-tetraphenyl-diimidazole and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-di One or more of the group consisting of imidazoles.

In a preferred embodiment, the free-radical oxime ester-based photopolymerization initiator includes, but is not limited to, 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid Oxime ester, 1-[6-(2-methylbenzyl)-9-ethylcarbazol-3-yl]-ethan-1-one-acetic oxime ester, 1-[6-(2- Methylbenzyl)-9-ethylcarbazol-3-yl]-butan-1-one-acetoxime ester, 1-[6-(2-methylbenzyl)-9-ethyl carbazol-3-yl]-propan-1-one-oxime acetate, 1-[6-(2-methylbenzyl)-9-ethylcarbazol-3-yl]-1-ring Hexyl-methane-1-one-oxime acetate, 1-[6-(2-methylbenzyl)-9-ethylcarbazol-3-yl]-(3-cyclopentyl)-propane- 1-keto-acetic oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-benzene thiophenyl)-(3-cyclohexyl) yl)-propane-1,2-dione-2-cyclohexylcarboxylate oxime ester, 1-[6-(2-methylbenzyl)-9-ethylcarbazol-3-yl]-(3 -Cyclopentyl)-propane-1,2-dione-2-acetic oxime ester, 1-(6-o-methylbenzyl-9-ethylcarbazol-3-yl)-(3-ring Amyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-benzyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate , 1-(6-o-methylbenzyl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oximecyclohexylcarboxylate, 1-(4-benzene Carboxylic diphenyl sulfide)-3-(cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-o-methylbenzyl-9-ethylcarbazol-3-yl )-(3-cyclopentyl)-propane-1,2-dione-2-o-toluic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane -1,2-Dione-2-cyclohexylcarboxylate, 1-(4-Thienylcarboxy-diphenylsulfide-4'-yl)-3-cyclopentyl-propan-1-one-acetic acid Oxime ester, 1-(4-benzyldiphenyl sulfide)-(3-cyclopentyl)-propane-1,2-dione-2-tallow acetate, 1-(6-nitro- 9-Ethylcarbazol-3-yl)-3-cyclohexyl-propan-1-one-acetoxime ester, 1-(6-o-methylbenzyl-9-ethylcarbazol-3-yl )-3-cyclohexyl-propan-1-one-acetic oxime ester, 1-(6-thienylcarbazol-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime Acetate, 1-(6-furfurfuryl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenyl Propane-1,3-dione-2-acetic oxime ester, 1-(6-furfuryl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-di Keto-2-acetic oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic oxime ester, 1-(6-furan furfuran) Carboxylic-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl) -Propane-1,2-dione-3-benzoic acid oxime ester, 1-(6-thienylcarbazol-3-yl)-(3-cyclohexyl)-propane-1, 2-diketo-2-acetoxyme ester, 2-[(benzyloxy)imino]-1-phenylpropan-1-one, 1-phenyl-1,2-propanedione-2- (Oxoacetoxy) oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane-1,2-dione-2-acetoxime, 1- (9,9-Dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propan-1-one-acetic oxime ester, 1-{4-[4-(thiophene-2-carboxylate yl)phenylthio]phenyl}-3-cyclopentylpropane-1,2-dione-2-acetic acid oxime ester, 1-[9,9-dibutyl-2- 1-[6-(2-benzyloxyimino)-3-cyclohexylpropyl-9- Ethylcarbazol-3-yl]octane-1,2-dione-2-benzoic acid oxime ester, 1-(7-Nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-acetate ester, 1-[6-(2-methyl) Benzyl)-9-ethylcarbazol-3-yl]-3-cyclopentyl-propan-1-one-benzoic acid oxime ester, 1-[7-(2-methylbenzyl) -9,9-Dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-acetic oxime and 1-[6-(furan-2-carbamoyl)-9- One or more of the group consisting of ethylcarbazol-3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxycarboxyme ester. Alternatively, the radical-type oxime ester-based photopolymerization initiator may be selected from commercially available CGI-325 manufactured by BASF JAPAN LTD., IRGACUREOXE01, IRGACUREOXE02, N-1919 manufactured by ADEKACORPORATION, and the like.

In a preferred embodiment, the alkylphenone-based photopolymerization initiators include, but are not limited to, benzalkonium dimethyl ketal-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, - One or more of the group consisting of an aminoacetophenone-based photopolymerization initiator and an acylphosphine oxide-based photopolymerization initiator.

More preferably, benzalkonium dimethyl ketal-based photopolymerization initiators include but are not limited to 2,2-dimethoxy-1,2-diphenylethan-1-one; Commercially available products of the ketal-based photopolymerization initiator include IRGACURE651 manufactured by BASF JAPAN LTD., and the like.

More preferably, α-hydroxyalkylphenone-based photopolymerization initiators include but are not limited to 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1-{4-[4-( One or more of the group consisting of 2-hydroxy-2-methyl-propanyl)-benzyl-1-phenyl}-2-methyl-propan-1-one; as α-hydroxyalkylphenone series Commercially available products of the photopolymerization initiator include IRGACURE184, DAROCUR1173, IRGACURE2959, and IRGACURE127 manufactured by BASF JAPAN LTD.

More preferably, α-aminoacetophenone-based photopolymerization initiators include but are not limited to 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl yl-2-dimethylamino-1-(4-morpholinophenyl)-butane Alkan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone , N,N-dimethylaminoacetophenone. As a commercial item of (alpha)-aminoacetophenone type photoinitiator, IRGACURE907, IRGACURE369, IRGACURE379 etc. by BASF JAPAN LTD. are mentioned.

More preferably, acylphosphine oxide-based photopolymerization initiators include but are not limited to 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl yl)-phenylphosphine oxide and/or bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide and the like. As a commercial item of an acylphosphine oxide type photoinitiator, TPO, 819 etc. by BASF JAPAN LTD. are mentioned.

Preferably, the first photopolymerization initiator (A1) is an imidazole-based photoinitiator.

When using the aforementioned photopolymerization initiators, the compounding amount is converted into solid content. In a preferred embodiment, the weight percentage of the photopolymerization initiator in the curable resin composition is 2 to 25 wt%, Preferably, it is 2.5 to 10 wt%.

In a preferred embodiment, the weight ratio of the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) is (0.5~5):(5~9.5).

Carboxyl-containing resin (B)

The carboxyl group-containing resin can make the curable resin composition an alkali-developable curable resin composition, and can obtain high resolution during development. The carboxyl group-containing resin (B) is not particularly limited, and known carboxyl group-containing resins used in curable resin compositions for solder resists and interlayer insulating layers can be employed.

In order to further improve the photocurability and development resistance of the curable composition, the carboxyl group-containing resin preferably has an ethylenically unsaturated bond in addition to the carboxyl group. More preferably, the above-mentioned ethylenically unsaturated double bond is a double bond derived from acrylic acid or methacrylic acid or their derivatives. or when the carboxyl-containing tree When the resin (B) does not have an ethylenically unsaturated bond, in order to improve the photocurability of the curable composition, a compound having one or more ethylenically unsaturated groups in the molecule (photoreactive monounsaturated group) may be added to the above-mentioned composition. body).

In a preferred embodiment, the carboxyl-containing resin containing carboxyl groups in the above-mentioned molecules and not having ethylenically unsaturated bonds in the molecule includes but is not limited to the following:

(1) Carboxyl group-containing compounds obtained by copolymerizing unsaturated carboxylic acids such as acrylic acid and methacrylic acid with compounds having unsaturated double bonds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, and isobutylene resin;

(2) The epoxy group of the copolymer of a compound having an unsaturated double bond and glycidyl (meth)acrylate, and an organic acid having one carboxyl group in one molecule and no ethylenically unsaturated bond, such as carbon A carboxyl-containing resin obtained by reacting an alkyl carboxylic acid with an atomic number of 2 to 17, an alkyl carboxylic acid containing an aromatic group, etc., and the generated secondary hydroxyl group reacts with a saturated or unsaturated polybasic acid anhydride;

(3) Hydroxyl-containing polymers such as olefin-based hydroxyl-containing polymers, acrylic polyols, rubber-based polyols, polyvinyl acetal, styrene allyl alcohol-based resins, celluloses, etc. are mixed with saturated or unsaturated The carboxyl-containing resin obtained by the reaction of polybasic acid anhydrides;

(4) Using bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin Reaction products of epoxy resins, bixylenol type epoxy resins and other diepoxy compounds with dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid, isophthalic acid, and saturated or Carboxyl-containing resin obtained by the reaction of unsaturated polybasic acid anhydrides;

(5) A carboxyl group-containing resin obtained by reacting a bifunctional epoxy compound with bisphenols such as bisphenol A and bisphenol F, and a saturated or unsaturated polybasic acid anhydride.

In a preferred embodiment, the carboxyl group-containing resin with carboxyl group in the aforementioned molecule and ethylenically unsaturated bond in the molecule includes but is not limited to the following:

(1) A polyfunctional epoxy compound having at least two epoxy groups in one molecule, such as a novolak-type epoxy resin, is reacted with an unsaturated monocarboxylic acid such as (meth)acrylic acid, and the generated hydroxyl group reacts with hexahydro-o Carboxyl-containing resins obtained by the reaction of saturated or unsaturated polybasic acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride;

(2) A polyfunctional epoxy compound having at least two epoxy groups in one molecule, such as a novolak-type epoxy resin, an unsaturated monocarboxylic acid such as (meth)acrylic acid, and a nonylphenol having in one molecule A compound having at least one alcoholic hydroxyl group and one reactive group other than the alcoholic hydroxyl group reacted with an epoxy group in one molecule, such as p-hydroxyphenethyl alcohol, is more preferred. After the compound reaction of the group, the carboxyl-containing resin obtained by reacting with saturated or unsaturated polybasic acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride;

(3) A part of the carboxyl group of a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and maleic acid and a photopolymerizable monomer such as methyl (meth)acrylate, and glycidyl (meth)acrylate, etc. A carboxyl group-containing resin obtained by the reaction of a compound having one epoxy group in one molecule and an ethylenically unsaturated double bond;

(4) Copolymers of unsaturated carboxylic acids such as (meth)acrylic acid and maleic acid, and photopolymerizable monomers such as methyl (meth)acrylate, and glycidyl (meth)acrylate, etc., have in one molecule A carboxyl-containing resin obtained by the reaction of one epoxy group with a compound with an ethylenically unsaturated double bond, and the resulting hydroxyl group reacted with saturated or unsaturated polybasic acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride ;

(5) Copolymers of unsaturated dibasic acid anhydrides such as maleic anhydride and photopolymerizable monomers such as methyl (meth)acrylate, and hydroxy (meth)acrylates such as 2-hydroxyethyl (meth)acrylate A carboxyl group-containing resin obtained by reacting an alkyl ester, etc.

In addition, the polyfunctional epoxy compound used in the synthesis of the above-mentioned resin has a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a bixylenol structure, a special In particular, in the case of a compound having a biphenyl novolak structure and a hydrogenated product thereof, the cured product of the obtained curable resin composition is preferably low in warpage and excellent in bending resistance.

It should be noted that the (meth)acrylate here is a term collectively referring to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions below.

Moreover, the acid value of the said carboxyl group containing resin becomes like this. Preferably it is the range of 20-200 mgKOH/g, More preferably, it is the range of 40-150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 20 mgKOH/g or more, the adhesiveness of the coating film can be obtained, and when a curable resin composition is formed, the alkali developability is favorable. In addition, when the acid value is 200 mgKOH/g or less, the dissolution of the exposed part by the developing solution can be suppressed, and the lines are not made thinner than necessary, and the exposed part and the unexposed part can be suppressed from being exposed to the developing solution without distinction. It dissolves and peels off, so that it becomes easy to draw a normal resist pattern.

The weight-average molecular weight of the above-mentioned carboxyl-containing resin varies according to the resin skeleton. Preferably, the weight-average molecular weight of the carboxyl-containing resin is 2,000 to 150,000. When the weight average molecular weight is 2000 or more, the non-stick performance is excellent, the moisture resistance of the coating film after exposure is good, the film reduction does not occur during development, and the resolution is good. In addition, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent. More preferably, the weight average molecular weight of the carboxyl group-containing resin is 5,000-100,000.

Photopolymerizable monomer (C)

The photopolymerizable monomer is a compound that insolubilizes the carboxyl group-containing resin or contributes to insolubilization in an alkaline aqueous solution after photocuring by irradiation with active energy rays, and the photopolymerizable monomer (C) can also be used as a curable It is used as a diluent for the resin composition.

As the above-mentioned photopolymerizable monomers, those commonly used in this field can be used. For example, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid cyclohexyl ester and other (meth)acrylic acid alkyl ester organic compounds; (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2 -Hydroxyalkyl (meth)acrylates such as hydroxypropyl esters Mono- or di(meth)acrylate organic compounds of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, bis(trimethylol) (meth)acrylate organic compounds of polyhydric alcohols such as ethylene oxide), bis(pentaerythritol), and trihydroxyethyl isocyanurate, or their ethylene oxide or propylene oxide adducts; (methyl) (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl acrylate and polyoxydi(meth)acrylate of bisphenol A; glycerol diglycidyl ether, triglyceride (meth)acrylates of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth)acrylates and the like.

The said photopolymerizable monomer (C) may be used individually by 1 type, and may be used in combination of 2 or more types. The compounding quantity of the said photopolymerizable monomer (C) is solid content conversion, Preferably, the weight percentage content of the photopolymerizable monomer (C) in the curable resin composition is 1-30 wt%. If it is 30% by weight or less, the surface will not be sticky, and the dryness to the touch will be good. Moreover, when it is 1 weight% or more, sufficient photocurability can be acquired at the time of exposure, and pattern formability is favorable. In order to further improve the curing time and the sufficient degree of photocuring of the cured product formed by the curable composition, more preferably, the weight percentage of the photopolymerizable monomer (C) is 2 to 20 wt %, more preferably 5 to 15 wt % %.

Thermosetting component (D)

In order to improve the heat resistance of the cured product formed from the curable resin composition, the curable resin composition preferably further includes a thermosetting component (D). In a preferred embodiment, the thermosetting component (D) includes but is not limited to blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclic carbonates One or more of the group consisting of a compound, a multifunctional epoxy compound, a multifunctional oxetane compound, and an episulfide resin.

In a preferred embodiment, the above-mentioned multifunctional epoxy compounds include but are not limited to epoxidized vegetable oil, bisphenol A epoxy resin, hydroquinone epoxy resin, bisphenol epoxy resin, and thioether ring Oxygen resin, brominated epoxy resin, o-cresol epoxy resin, novolak type epoxy resin, biphenol novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, shrinkage Glycerylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin , Tetraphenolethane epoxy resin, Heterocyclic epoxy resin, Diglycidyl phthalate resin, Tetraglycidyl xylenol ethane resin, Naphthyl-containing epoxy resin, Dicyclopentadiene Skeleton epoxy resin, glycidyl methacrylate copolymer epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin, epoxy modified polybutadiene rubber derivative , Carboxyl-terminated liquid nitrile rubber modified epoxy resin (CTBN modified epoxy resin), bixylenol type and/or biphenol type epoxy resin. These epoxy resins may be used alone or in combination of two or more. Among them, bisphenol-type epoxy resins are particularly preferred.

In a preferred embodiment, the multifunctional oxetane compounds include, but are not limited to, multifunctional oxetane compounds, etherates of resins with hydroxyl groups, and unsaturated mono-unsaturated oxetane rings. One or more of the group consisting of copolymers with alkyl (meth)acrylates.

More preferably, polyfunctional oxetanes include, but are not limited to, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3 -Oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl- 3-oxetanyl) methyl ester, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl methacrylate) ) methyl esters, or one or more of the group consisting of their oligomers or copolymers.

More preferably, etherates of resins with hydroxyl groups include, but are not limited to, oxetanol, novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, resorcinol calix Aromatic compounds, or silsesquioxanes.

Episulfide resins having a plurality of cyclic sulfide groups include, but are not limited to, YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation, YSLV-120TE manufactured by Todo Chemical Co., Ltd., and the like. In addition, episulfide resins etc. in which the oxygen atoms of the epoxy groups of the novolak-type epoxy resins are replaced with sulfur atoms can also be used in the same synthesis method. Examples of commercially available epoxy resins include jER828, 806, 807, YX-8000, 8034, and jER834 manufactured by Mitsubishi Chemical Corporation, and YD-128, YDF-170, and ZX- 1059, ST-3000, 830, 835, 840, 850, N-730A, N695 manufactured by DIC Corporation and RE-306 manufactured by Nippon Kayaku Corporation.

In order to improve the curing rate of the curable composition and shorten the dry time, in a preferred embodiment, in addition to the above-mentioned thermosetting resin components, the curable resin composition of the present invention further includes a thermosetting catalyst. Any compound that can achieve the above-mentioned object can be used as a thermal curing catalyst. More preferably, the above-mentioned thermally curable catalyst includes, but is not limited to, one or more of the group consisting of imidazole derivatives, amine compounds, hydrazine compounds, organic phosphines, melamines, guanamine compounds and s-triazine compounds. Wherein imidazole derivatives include but are not limited to imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl - One or more of the group consisting of 2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds include but are not limited to dicyandiamide, benzyl dicyandiamide Methylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethyiamine One or more of the group consisting of methylbenzylamine; hydrazine compounds including but not limited to dihydrazine adipate and/or dihydrazine sebacate; organophosphorus including but not limited to triphenylphosphine. Guanamine compounds include, but are not limited to, guanamine and/or benzoguanamine). S-triazine derivatives including but not limited to 2,4-diamino yl-6-methyl-1,3,5-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-s-triazine˙isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine˙ One or more of the group consisting of isocyanuric acid adducts.

other ingredients

In order to further improve the comprehensive properties of the curable resin composition, preferably, the curable resin composition further includes additives, more preferably, the additives are selected from thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, Flame retardant, antistatic agent, antiaging agent, antibacterial/antifungal agent, antifoaming agent, leveling agent, filler, thickener, adhesion imparting agent, thixotropy imparting agent, colorant, sensitizer, One or more of the group consisting of a hydrogen donor and a solvent.

filler

The curable resin composition of the present invention may contain a filler (inorganic filler). The filler is used in order to suppress curing shrinkage of the cured product of the curable resin composition and to improve characteristics such as adhesiveness and hardness. Examples of fillers include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, Boron nitride, Noyburg silica, etc.

The average particle diameter (D50) of the filler is preferably 1 μm or less, more preferably 0.7 μm or less, and further preferably 0.5 μm or less. When the average particle diameter exceeds 1 μm, the curable resin composition may become cloudy, which is not preferable depending on the application. The average particle diameter (D50) can be measured by a laser diffraction/scattering method. When the average particle diameter is in the above-mentioned range, the refractive index becomes close to the resin component, and the transmittance improves.

solvent

As an organic solvent, a well-known thing can be used. In addition, an organic solvent may be used individually by 1 type, and may be used in mixture of 2 or more types. Preferably, the organic solvent includes but is not limited to the following one One or more: ketone solvents such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene and tetratoluene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol Alcohol, 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 glycol ether solvents; ethyl acetate , butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Ester solvents such as methyl ether acetate and propylene carbonate; aliphatic hydrocarbon solvents such as octane and decane; petroleum solvents such as petroleum ether, naphtha, and solvent naphtha, etc.

The organic solvent is generally used for the purpose of preparing a composition, forming a dry film, and adjusting the viscosity at the time of coating on a printed circuit board. Therefore, content of an organic solvent can be suitably changed according to the objective.

Sensitizer

The sensitizers can include (but are not limited to): anthracene photoinitiators, coumarin photoinitiators, thioxanthone photoinitiators, acridine photoinitiators and other photoinitiators known to those skilled in the art initiator.

In a preferred embodiment, the anthracene compounds include but are not limited to: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3 -Dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10- bis(methyl 4-chlorobutyrate), 2-{3-[(3-ethyloxetan-3-yl)methoxy]-3-oxopropyl}anthracene-9,10- Diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,10-bis( 2-Hydroxyethylmercapto)anthracene, 9,10-bis(3-hydroxy-1-propylmercapto)anthracene.

In a preferred embodiment, the coumarin compounds include but are not limited to: 3,3'-carbonylbis(7-diethylamine coumarin), 3-benzyl-7-diethylamine incense Bean, 3,3'-carbonylbis(7-methoxyl) coumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7-(diethylamino)-4 - Methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3-benzyl-7-methoxycoumarin. These coumarin-based compounds may be used alone or in combination of two or more.

In a preferred embodiment, thioxanthone compounds include but are not limited to: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone Ketone (isopropylthioxanthone), 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, Diisopropyl thioxanthone.

In a preferred embodiment, acridine compounds include but are not limited to: 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methyl phenyl acridine, 9-o-chlorobenzene Acridine, 9-o-fluorophenylacridine, 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-( 3-Chlorophenyl)acridine, 1,7-bis(9-acridine)heptane, 1,5-bis(9-acridinepentane), 1,3-bis(9-acridine)propane.

The above sensitizers can be used alone or in combination. In the curable resin composition, the weight percentage of the sensitizers is 0.01-10 wt %, preferably 0.01-5 wt %. The content of the sensitizer includes, but is not limited to, the above range, and it is beneficial to further improve the sensitivity of the curable resin composition if it is limited to the above range.

hydrogen donor

As mentioned above, the curable resin composition of the present invention is characterized in that the combination of a specific photoinitiator can improve the curing performance of the composition, and it is particularly preferable to use an imidazole compound in combination with the compound of the general formula (1). In this case, in order to improve the sensitivity, the curable composition preferably further includes a hydrogen donor. Biimidazole compounds are cracked by light, and the monoimidazole free radicals produced are larger in size, and the steric hindrance effect makes the activity less, so it is difficult to initiate the polymerization of monomers alone. The active hydrogen on the hydrogen donor body is captured, new active free radicals are generated, and the monomer polymerization is initiated.

As long as it is a hydrogen donor having the above-mentioned properties, there is no particular limitation in terms of specific types, which may include (but are not limited to): amine compounds, carboxylic acid compounds, mercapto group-containing organosulfur compounds or alcohol compounds. These compounds may be used alone or in combination of two or more of them.

Amine compounds are not particularly limited, and may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as methyl 4-dimethylaminobenzoate Ester, Ethyl 4-Dimethylaminobenzoate, Isoamyl 4-Dimethylaminobenzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, 2-Dimethylaminoethylbenzoate, N , N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc.

Carboxylic acid compounds are not particularly limited, and can include (but are not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid Acetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

The organosulfur compounds containing mercapto groups are not particularly limited, and may include (but are not limited to): 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis( 3-mercaptobutyrate), 1,2-propanediol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), Octanediol bis(3-mercaptobutyrate), Trimethylolpropane tris(3-mercaptobutyrate), Pentaerythritol tetrakis(3-mercaptobutyrate), Dipentaerythritol hexa(3-mercaptobutyrate) , ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate) ), octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(2-mercaptopropionate) ester), ethylene glycol bis(3-mercaptoisobutyrate), 1,2-Propanediol bis(3-mercaptoisobutyrate), Diethylene glycol bis(3-mercaptoisobutyrate), Butylene glycol bis(3-mercaptoisobutyrate), Octanediol bis( 3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), pentaerythritol tetra(3-mercaptoisobutyrate), dipentaerythritol hexa(3-mercaptoisobutyrate), Ethylene glycol bis(2-mercaptoisobutyrate), 1,2-propanediol bis(2-mercaptoisobutyrate), diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis( 2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane tris(2-mercaptoisobutyrate), pentaerythritol tetrakis(2-mercaptoisobutyrate) , dipentaerythritol hexa(2-mercaptoisobutyrate), ethylene glycol bis(4-mercaptoisovalerate), 1,2-propanediol bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptoisovalerate) - mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane tris(4-mercaptovalerate), pentaerythritol tetra (4-mercaptovalerate), dipentaerythritol hexa(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), 1,2-propanediol bis(3-mercaptovalerate), bis(3-mercaptovalerate) Ethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane tris(3-mercaptopentanate) aliphatic secondary polyfunctional thiol compounds such as ester), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate); aromatic secondary polyfunctional thiol compounds, such as o-phenylene Di(1-mercaptoethyl) phthalate, bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, bis(3-mercaptoisobutyl phthalate) )Wait.

Alcohol compounds are not particularly limited, and may include (but are not limited to): methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentanol, n-hexanol, cyclohexanol, Ethylene glycol, 1,2-propanediol, 1,2,3-propanetriol, benzyl alcohol, phenethyl alcohol, etc.

In the curable resin composition, the weight percentage of the hydrogen donor is 0.01-20 wt %, preferably 0.01-10 wt %. When the content of the hydrogen donor is within the above range, it is advantageous to adjust the sensitivity of the curable resin composition.

Colorant

The curable resin composition of this invention can mix|blend a coloring agent. As the colorant, known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and dyes may be used. Specifically, those with the following Dye Index (C.I.; issued by The Society of Dyers and Colourists) number can be cited. Among them, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferable that no halogen is contained.

Red Colorant:

Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, parallel, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridine. As the pyridone series, specifically, the following can be exemplified.

Monoazo series: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Disazo series: Pigment Red 37, 38, 41.

Monoazo Lake Series: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53 : 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue Colorant:

Examples of blue colorants include phthalocyanine-based and anthraquinone-based colorants. Pigment-based colorants are compounds classified as pigments, and specific examples thereof include the following: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2 , Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

As the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Green Colorant:

As the green colorant, there are also phthalocyanine-based, anthraquinone-based, and combined-based colorants. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds such as phthalocyanine green can also be used.

Yellow Colorant:

As the yellow colorant, there are monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, anthraquinone-based, and the like, and specifically, the following are exemplified.

Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo series: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

Disazo series: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, in order to adjust the color tone, colorants such as purple, orange, brown, black, etc. may be added.

Specific examples include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16. C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. 51. C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Black 1, C.I. Pigment Black 7, etc.

In a preferred embodiment, the colorant can be properly compounded. In the curable composition, the weight ratio of the carboxyl-containing resin (B) or the thermosetting component (D) to the colorant is greater than 100:10, more preferably 100: (0.1~5).

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

The curable resin composition of this invention can be used for forming the pattern layer of the permanent film of the printed wiring board, such as a solder resist layer, a cover layer, an interlayer insulating layer, etc., and it is especially useful for forming a solder resist layer. In addition, since a cured product having excellent coating film strength can be formed even if it is a thin film, the curable resin composition of the present invention can also be suitably used for printed wiring boards requiring thinning, such as IC package substrates (printed boards used in IC packages). The formation of pattern layers in circuit boards). Furthermore, the cured product obtained from the curable resin composition of the present invention has the advantages of high elastic modulus and low CTE (coefficient of expansion), and thus can be suitably used for forming a pattern layer in an IC package substrate having a thin overall thickness and insufficient rigidity.

The curable resin composition of the present invention may be in the form of a dry film including a carrier film (support) and a resin layer formed of the curable resin composition described above formed on the carrier film. In the case of dry film formation, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and is passed through a comma coater, knife coater, lip coater, bar A rod coater, squeeze coater, reverse coater, transfer rollcater, gravure coater or spray coater is applied to the carrier film Uniform thickness, the film is usually obtained by drying at a temperature of 50~130℃ for 1~30min. The thickness of the coating film is not particularly limited, but is usually appropriately selected in the range of 1 to 150 μm, preferably 10 to 60 μm, in terms of the film thickness after drying.

As the carrier film, a plastic film can be used, preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, etc. film and other plastic films. The thickness of the carrier film is not particularly limited, and is usually appropriately selected within the range of 10 to 150 μm.

After forming the resin layer of the curable resin composition of the present invention on the carrier film, in order to prevent dust and the like from adhering to the surface of the resin layer, it is more preferable to laminate a peelable cover film on 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, as long as the adhesive force between the resin layer and the cover film is smaller than that between the resin layer and the carrier when the cover film is peeled off film adhesion.

The printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or the resin layer of the dry film. As a method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and dip coating, flow coating, roll coating, or bar coating is used. Method, screen printing method or curtain coating method, etc. are applied to the substrate, and then the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60~100 ° C to form a non-stick resin layer. . In addition, in the case of a dry film, the resin layer is formed on the base material by bonding the resin layer to the base material using a laminator or the like so that the resin layer is in contact with the base material, and then peeling off the carrier film.

As the above-mentioned base material, in addition to printed wiring boards and flexible printed wiring boards in which circuits are previously formed by copper or the like, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass- Polyimide, glass cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin˙polyethylene˙polyphenylene oxide (polyphenylene oxide)˙ All grades (FR-4, etc.) of copper-clad laminates for high-frequency circuits such as cyanate esters, etc., as well as copper-clad laminates, metal substrates, polyimide films, PET films, polyethylene naphthalate Ester (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.

For volatilization drying after applying the curable resin composition of the present invention, a hot-air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. (a device having a heat source of an air heating method using steam is used, and the air in the dryer can be made to dry). The method of hot air convective contact and the method of blowing to the support through a nozzle) were carried out.

After the resin layer is formed on the substrate, it is selectively exposed with active energy rays through a photomask with a predetermined pattern, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt % sodium carbonate aqueous solution), Thus, a pattern of the cured product is formed. 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, and then irradiated with active energy rays, or only heated and cured to be finally cured (completely cured), thereby forming Cured film excellent in various properties such as adhesion and hardness.

The exposure device used for the above-mentioned active energy ray irradiation may be any device that is equipped with a high-pressure mercury lamp, an LED light source, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, etc. and irradiates ultraviolet rays in the range of 350 to 450 nm. In addition, a direct drawing device (eg, a laser direct imaging device that directly draws an image with a laser using CAD data from a computer) can also be used. As the light source or laser source of the direct drawing machine, as long as the maximum wavelength is in the range of 350~410nm. The exposure amount for forming an image varies depending on the film thickness and the like, but is usually within a range of 10 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .

As the above-mentioned developing method, a dipping method, a rinsing method, a spraying method, a brushing method, etc. can be used, and as the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, etc. can be used , amines and other alkaline aqueous solutions.

The curable resin composition of the present invention can be used not only for applications in which a pattern of a cured film is formed by the above-mentioned developer, but also in applications in which no pattern is formed, for example, mold applications (sealing applications).

Another aspect of the present application also provides a solder mask, which is formed by curing the curable resin composition provided by the present application. The above compositions have excellent curability both in thick coatings and in systems with high colorant content, and at the same time have high resolution and good heat resistance, chemical resistance and adhesion. Therefore, the solder resist film prepared by using it has excellent heat resistance, chemical resistance, adhesion and high resolution.

Yet another aspect of the present application also provides a printed circuit board including a solder mask, the solder mask including the solder mask provided by the present application. Because the solder resist film provided by the present application has excellent heat resistance, chemical resistance, adhesion and high resolution. Therefore, the above-mentioned solder resist film is arranged on the printed circuit board, which greatly improves the appearance of the printed circuit board and reduces the amount of colorant.

Another aspect of the present application also provides an interlayer insulating material, which is formed by curing the curable resin composition provided by the present application. The above compositions have excellent curability both in thick coatings and in systems with high colorant content, and at the same time have high resolution and good heat resistance, chemical resistance and adhesion. Therefore, the interlayer insulating material prepared by using it has excellent heat resistance, chemical resistance, adhesion and high resolution.

The present application will be described in further detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by the present application.

<Preparation of curable resin composition>

With the compositions (parts by weight) shown in Tables 1 and 2, each component was premixed with a mixer, and then kneaded with a three-roll mill to prepare a curable resin composition. Wherein, the photopolymerization initiator in the comparative example adopts 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone commonly used in the current technology as a comparison. The present invention will be further specifically described with reference to Comparative Examples, but the present invention is not limited to the following Examples.

Table 1

Table 2

The meanings represented by the component codes in Tables 1 and 2 are shown in Table 3.

table 3

Evaluation of properties of curable resin compositions

1. <Sensitivity evaluation>

The curable resin compositions of Examples and Comparative Examples were applied onto a copper-filled substrate at a thickness of about 25 μm by a screen printing method, and were dried in a hot air circulation drying oven at 80° C. for 30 minutes. After the dried substrate was left to reach room temperature, the exposure equipment (ELS106SA) equipped with a metal halide lamp was used, respectively, with a 150mj/ ^cm2 and a 405nm LED exposure machine (RW-UVAP202-20gl) at 200mj/ ^cm2 in a stepwise manner. The dried coating film was exposed by an exposure meter (Stuffer 21 grade), and the pattern of the stepwise exposure meter remaining after development (1 wt % Na ₂ CO ₃ aqueous solution, 30° C., 0.2 MPa) for 60 s was read. The higher the number of stages of the residual film, the higher the sensitivity of the curable composition.

2. <Appearance of cured coating>

The composition of each said Example and the comparative example was apply|coated to the whole surface of the copper foil board|substrate with a circuit thickness of 35 micrometers in which the pattern was formed by the screen printing method, and it cooled to room temperature naturally. The curable resin composition was exposed to light at an optimum exposure amount of 150 mj/cm ² , and then thermally cured at 150° C.×60 min to obtain a cured coating film. Visually observe the appearance of the cured coating;

○: The coating is smooth and flat without shrinkage

×: Coating appearance is poor, with local shrinkage

3. <resolution>

The curable resin compositions of the aforementioned Examples and Comparative Examples were applied over the entire surface of a copper-filled substrate by screen printing so that the film thickness after drying was 25 μm, and dried at 80° C. for 30 minutes. After the dried substrate was left to reach room temperature, the substrate was subjected to 150 mJ using an exposure device (ELS106SA) equipped with a high-pressure mercury lamp and a dedicated negative film prepared so as to obtain a solder resist pattern with a width of 30 μm to 100 μm every 10 μm. /cm ² exposure, 60s development was performed with a 1wt% sodium carbonate aqueous solution at 30°C under the condition of a spray pressure of 0.2MPa, and a resist pattern for resolution evaluation was obtained.

4. <Substrate manufacturing method for evaluation of soldering heat resistance, acid resistance and alkali resistance>

The curable resin compositions of the aforementioned Examples and Comparative Examples were applied over the entire surface of the patterned copper foil substrate by screen printing, dried at 80° C. for 30 min, and naturally cooled to room temperature. The curable resin composition was exposed at an optimum exposure amount of 150 mj/cm ² , and developed with a 1 wt % sodium carbonate aqueous solution at 30° C. under the condition of a spray pressure of 0.2 MPa for 60 s to obtain a resist pattern. This board|substrate was heated and hardened at 130 degreeC for 60 minutes, and it was set as the board|substrate for evaluation.

<Soldering heat resistance>

The cured paint film is coated with rosin-type flux and immersed in a lead-tin furnace at 288°C for 30s. Scrub the surface with butyl glycol ether, and pull 3M tape (model 610#) three times. If there is no oil drop, it means heat resistance is OK, otherwise NG.

<Acid resistance>

The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 20 minutes, and the impregnation, the elution of the coating film, and further the peeling due to tape peeling were visually confirmed.

○: No change observed

△: Only slightly changed

×: The coating film swells or swells and falls off

<Alkaline resistance>

The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 20 minutes, and the impregnation, the elution of the coating film, and the peeling due to tape peeling were confirmed by visual inspection.

○: No change observed

△: Slightly swollen

×: The coating film swells and falls off

<Solvent resistance>

The evaluation substrate was immersed in propylene glycol monomethyl ether at room temperature for 20 minutes, and the impregnation, the elution of the coating film, and the peeling due to tape peeling were confirmed visually.

○: No change observed

△: Slightly swollen

×: The coating film swells and falls off

5. <Tightness test>

The curable resin compositions of Examples and Comparative Examples were applied by screen printing to a copper-filled substrate and polyimide that had been polished by a brush machine at a thickness of about 25 μm, and dried in a hot air circulating drying oven at 80°C. 30min. After the dried substrate was left to reach room temperature, the curable resin composition was exposed at an optimum exposure amount of 150 mj/cm ² , and then thermally cured at 150° C.×60 min to obtain a cured coating film.

According to the national standard "GBT9286-1998 Scratch test of paint and varnish film", the adhesion test is carried out. The test method is: use a hundred grid knife, the width of the knife edge is about 10mm~12mm, every 1mm~1.2mm is the interval, a total of 10 When the straight line is drawn, 10 straight line knife marks with the same interval will appear. When the straight line knife mark is drawn at the vertical position, it becomes a 10×10 square of 100 squares. Only cut on the coating, otherwise the test will not hold. When the 100 grid knife is finished, use the 3M The Transparent Tape 600 tape produced by the company is tested to see if it will fall off. First, stick the tape to the 100 grid position, press down with your fingers to stick the tape tightly, and then tear off the tape with an instant force to see if the paint on the material has fallen off. Phenomenon.

Rating Methods and Criteria:

Grade 0: The edges of the cut are completely smooth, and the edges of the lattice do not have any flaking.

5%。 Level 1: Small pieces are peeled off at the intersection of the incisions, and the actual breakage is in the cross-cut area

5%.

Grade 2: The edges and/or intersections of the incision are peeled, and the area is greater than 5% to 15%.

Grade 3: Partial peeling or whole large peeling off along the edge of the incision, or part of the grid is peeled off in a whole piece, and the peeling area exceeds 15%~35%.

Level 4: The edge of the incision is largely peeled off/or some squares are partially or completely peeled off, and the area is greater than 35% to 65% of the cut area.

Level 5: There are pieces of paint peeling off at the edges and intersections of the scribed lines, and the total peeling area is greater than 65%.

The evaluation results are shown in Table 4.

Table 4

As can be seen from the results shown in Table 4, by combining the first bisimidazole-based photopolymerization initiator, the oxime ester-based first photopolymerization initiator, the alkylphenone-based first photopolymerization initiator, and the acylphosphine oxide-based first photopolymerization initiator Any one of the photopolymerization initiators is specifically combined with the second photopolymerization initiator represented by the general formula (I), especially the embodiment of the combination of the bisimidazole-based photoinitiator and the general formula (I). The curable resin composition is excellent in curability and excellent in other comprehensive properties.

In addition, experimental studies have found that the first photopolymerization initiator (A1) or the second photopolymerization initiator (A2) alone has the problem of low sensitivity and poor development in the curable resin composition. Therefore, in the present invention Comparative examples using the first photopolymerization initiator (A1) or the second photopolymerization initiator (A2) alone are not provided.

It should be noted that the terms "first", "second", etc. in the description of the present application and the scope of the patent application are used to distinguish similar objects, and are not necessarily used to describe a specific sequence or sequence. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein can, for example, be practiced in sequences other than those described herein.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (11)

A curable resin composition, characterized in that the curable resin composition includes a photopolymerization initiator (A), a carboxyl group-containing resin (B) and a photopolymerizable monomer (C), and the photopolymerization initiator (A) includes A first photopolymerization initiator (A1) and a second photopolymerization initiator (A2), wherein the first photopolymerization initiator (A1) is selected from radical-type oxime ester-based photopolymerization initiators, radical-type imidazoles One or more of the group consisting of a photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator, and the second photopolymerization initiator (A2) has the following properties: The structure shown in formula (I):

In formula (I), A represents hydrogen, nitro, halogen or -CO-CR ₂ R ₃ R ₄ group; two R ₁ are each independently selected from hydrogen, C ₁ ～C ₁₀ straight-chain alkyl or C ₃ ~C ₁₀ branched alkyl, or C ₂ ~C ₁₀ alkenyl, or two of the R ₁ form a cyclic structure; R ₂ and R ₃ independently represent a C ₁ ~C ₁₀ straight chain Alkyl or C ₃ -C ₁₀ branched chain alkyl; R ₄ represents a photoactive group. The curable resin composition according to claim 1, wherein in the formula (I), two R ₁ are each independently selected from hydrogen, C ₁ -C ₆ straight-chain alkyl or C ₃ -C ₆ The branched chain alkyl or C ₂ ~C ₆ alkenyl, or two of the R ₁ form a four-membered ring, a five-membered ring or a six-membered ring. The curable resin composition according to claim 1 or 2, wherein in the formula (I), R ₂ and R ₃ independently represent a C ₁ -C ₆ straight-chain alkyl group or C ₃ -C ₆ branched chain alkyl. The curable resin composition according to claim 3, wherein in the formula (I), the R ₄ is a hydroxyl group or an N-morpholino group. The curable resin composition according to claim 4, wherein the A is hydrogen or a -CO-CR ₂ R ₃ R ₄ group, and in the substituent -CO-CR ₂ R ₃ R ₄ group R ₂ , R ₃ and R ₄ of claim 1 have the same definitions. The curable resin composition according to claim 1, wherein the weight ratio of the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) is (0.5 to 5): (5 ~9.5). The curable resin composition according to any one of claims 1 to 6, wherein the curable resin composition further includes a thermosetting component (D). The curable resin composition according to claim 7, wherein the thermosetting component (D) is selected from the group consisting of blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, and carbodiimide One or more of the group consisting of resins, cyclic carbonate compounds, multifunctional epoxy compounds, multifunctional oxetane compounds, and episulfide resins. A solder resist film, characterized in that, the solder resist film is formed by curing the curable resin composition according to any one of Claims 1 to 8. A printed circuit board, comprising a solder mask, characterized in that the solder mask comprises the solder mask described in claim 9. An interlayer insulating material, characterized in that the interlayer insulating material is formed by curing the curable resin composition according to any one of claims 1 to 8.