CN111684011A - Resist composition and resist film - Google Patents

Abstract

The invention aims to provide a resist composition which has excellent storage stability and is excellent in screen printing performance, definition, low warpage, flexibility, chemical resistance and flame retardance. The present invention relates to a resist composition comprising: a biphenyl aralkyl type epoxy resin (A), an acid anhydride curing agent (B) containing a carboxylic anhydride (B1) and a carboxylic anhydride modified product (B2), and an extender pigment (C); the resist composition contains 20 to 100 parts by mass of the acid anhydride curing agent (B) and 10 to 200 parts by mass of the extender pigment (C) based on 100 parts by mass of the solid content of the biphenyl aralkyl epoxy resin (A).

Description

Resist composition and resist film

technical field

The present invention relates to a resist composition and resist film having good storage stability and excellent screen printability, clarity, low warpage, flexibility, chemical resistance and flame retardancy.

Background technique

The purpose of solder resist is to prevent solder from adhering to unnecessary parts and to protect circuits when soldering components to a printed wiring board. The cured film formed from the resist composition used for this application needs to satisfy the adhesion to the substrate, flame retardancy, electrical insulation, solder heat resistance, chemical resistance (solvent resistance, alkali resistance) and acid resistance) and plating resistance and other characteristics. In addition, in recent years, the demand for high-definition and flexible circuit boards has been increasing, and flexibility and low warpage properties after coating and curing are also essential.

Conventionally, pattern formation by resist composition generally involves exposure and etching of a photosensitive composition to form a pattern, but a large amount of chemical solutions such as photoresist composition, developer, etching solution, and stripping solution are required. , and requires complicated processes. Therefore, it is required that a high-definition pattern film can be formed by screen printing without an exposure step.

In this regard, for example, Patent Document 1 proposes a resist composition for printing containing (A) a biphenyl aralkyl type epoxy resin, and (B) at least an amine value in the range of 100 to 500 mgKOH/g. An amine-based curing agent, (C) particulate silica having an average primary particle diameter in the range of 1 to 100 nm, (D) a flaky extender pigment, and (E) an organic solvent, wherein the epoxy resin (A) The content of the component (D) is 0.1 to 100 parts by mass based on 100 parts by mass of the resin solid content.

However, in pursuit of performance improvement, the above-mentioned resist composition for printing has insufficient storage stability, and in addition, any performance in screen printability, clarity, low warpage, flexibility, and flame retardancy is required. improvement on.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2017-82089

SUMMARY OF THE INVENTION

The problem to be solved by the invention

An object of the present invention is to provide a resist composition having good storage stability and excellent screen printability, clarity, low warpage, flexibility, chemical resistance, and flame retardancy.

means of solving problems

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have found that the biphenyl aralkyl type epoxy resin (A), the alicyclic carboxylic acid anhydride (b1) and the alicyclic carboxylic acid anhydride are contained in a specific ratio. The resist composition of the acid anhydride-based curing agent (B) of the modified product (b2) and the extender pigment (C) can solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention relates to a resist composition containing:

A biphenyl aralkyl type epoxy resin (A) represented by the following general formula (I);

An acid anhydride-based curing agent (B) comprising a carboxylic acid anhydride (b1) and a carboxylic acid anhydride modified product (b2); and

Extender Pigments (C),

The resist composition contains 20 to 100 parts by mass of the acid anhydride-based curing agent (B) and 10 to 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A) 200 parts by mass of the extender pigment (C);

[hua 1]

(in the formula, n represents the number of repetitions of 1 to 10).

Invention effect

The resist composition of the present invention is excellent in storage stability, and can form a resist film excellent in all of screen printability, clarity, low warpage, flexibility, chemical resistance, and flame retardancy.

Detailed ways

The resist composition of the present invention contains: a biphenyl aralkyl type epoxy resin (A); an acid anhydride-based curing agent (B) containing a carboxylic acid anhydride (b1) and a carboxylic acid anhydride modified product (b2); and an extender pigment (C).

Biphenyl aralkyl type epoxy resin (A)

The biphenyl aralkyl type epoxy resin (A) used in the present invention is usually derived from a compound having a phenol skeleton such as a biphenyl derivative, a phenol compound and a naphthol compound, and contains two or more epoxy groups in the molecule. A polyfunctional epoxy resin represented by the general formula (I).

[hua 2]

(in the formula, n represents the number of repetitions of 1 to 10).

The phenol aralkyl type resin which is a raw material of the above-mentioned biphenyl aralkyl type epoxy resin (A) can be obtained, for example, by using 4,4'-bismethoxymethylbiphenyl or 4,4'-bishalomethyl. It is obtained by the condensation reaction of substituted methylene biphenyl compounds such as base biphenyl and phenolic compounds under acidic conditions. Next, the compound of the above-mentioned general formula (I) can be obtained by reacting the above-mentioned phenol aralkyl-type resin with a halogenated epoxide such as epichlorohydrin and β-methyl epichlorohydrin to glycidyl.

As the biphenyl aralkyl type epoxy resin (A), "NC-3000", "NC-3000-L", "NC3000-H", and "NC3000-FH" manufactured by Nippon Kayaku Co., Ltd. can be used, for example. and "NC3100" and other commercial products.

In addition, in the biphenyl aralkyl type epoxy resin represented by general formula (1), the content ratio of the biphenyl aralkyl type epoxy resin of n=1 is as follows: "NC3000-FH" is about 15 ~20 mass%, "NC3000-H" is about 20-25 mass%, "NC3000" is about 30-40 mass%, "NC3000L" is about 40-50 mass%, "NC3100" is about 55-65 mass% .

Acid anhydride curing agent (B)

The acid anhydride-based curing agent (B) used in the present invention includes a carboxylic acid anhydride (b1) and a modified product (b2) of a carboxylic acid anhydride.

Carboxylic anhydride (b1) :

As carboxylic acid anhydride (b1), for example, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl base hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, chloro bridge anhydride, himic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl- 3-cyclohexene-1,2-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, chlorine Anhydrides of alicyclic carboxylic acids such as Chlorendic acid and methylendomethylenetetrahydrophthalic acid; dodecenyl succinic anhydride, polyazelaic anhydride, polysebacic anhydride, polydodecanedioic acid Acid anhydrides of aliphatic carboxylic acids such as acid anhydrides; acid anhydrides of aromatic carboxylic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyl tetracarboxylic anhydride, etc. As a commercial product of the carboxylic acid anhydride (b1), "KayahardMCD" (methyl-5-norbornene-2,3-dicarboxylic acid anhydride) manufactured by Nippon Kayaku Co., Ltd., manufactured by Nippon Chemical Co., Ltd. "Rikacid HH" (hexahydrophthalic anhydride), "Rikacid MH-T" (methylhexahydrophthalic anhydride), "Rikacid MH-700" (methylhexahydrophthalic anhydride) Wait.

Modified product (b2) of carboxylic anhydride :

As the modified product (b2) of the carboxylic acid anhydride, for example, a modified product of an alicyclic carboxylic anhydride, a modified product of an aliphatic carboxylic anhydride, and a modified product of an aromatic carboxylic acid anhydride can be mentioned. Specifically, esters of alicyclic carboxylic anhydrides and (poly)alkylene glycols, esters of aliphatic carboxylic anhydrides and (poly)alkylene glycols, modified aromatic carboxylic anhydrides and (poly)alkylene glycols can be mentioned. ) esters of alkylene glycols, etc. As (poly)alkylene glycol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, a block product of polyethylene glycol, and polypropylene glycol, etc. are mentioned, for example. As a commercial product of the modified product (b2) of carboxylic acid anhydride, "Rikacid HF-08" (ester of alicyclic carboxylic acid anhydride and (poly)alkylene glycol) manufactured by Nippon Chemical Co., Ltd., "Rikacid TMEG-100" (ester of aromatic carboxylic acid anhydride and ethylene glycol) and the like.

In the acid anhydride-based curing agent (B), the use ratio (mass ratio) of the carboxylic acid anhydride (b1) and the carboxylic acid anhydride modified product (b2) is two components from the viewpoints of curability, flexibility, and chemical resistance. Based on the total solid content of , it is desirable that (b1)/(b2)=5/5 to 1/9, preferably 4/6 to 2/8.

In addition, the usage-amount of the acid anhydride type curing agent (B) is based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A) from the viewpoint of curability, flexibility, chemical resistance, and flame retardancy It is 20-100 mass parts as a basis, Preferably it is 40-90 mass parts.

Extender Pigment (C)

Examples of the extender pigment (C) used in the present invention include clay, silica, fumed silica, barium sulfate, talc, calcium carbonate, white carbon, diatomaceous earth, aluminum magnesium carbonate flakes, and mica flakes Wait.

The use amount of the extender pigment (C) is based on the solid content of the biphenyl aralkyl type epoxy resin (A) 100 from the viewpoint of storage stability, low warpage, flexibility, chemical resistance and flame retardancy. It is 10-200 mass parts based on a mass part, Preferably it is 30-180 mass parts.

In the present invention, it is particularly desirable to contain the following fumed silica (c1) and barium sulfate (c2) from the viewpoint of improving storage stability, low warpage, flexibility, chemical resistance, and flame retardancy and talc (c3) as extender pigment (C).

Fumed silica with an average primary particle size of 1 to 20 nm (c1)

Fumed silica (c1) is an amorphous glassy spherical non-porous silica synthesized by vaporizing silicon chloride in a high temperature hydrogen flame by gas phase reaction, and having an average primary particle size of 1 to 20 nm , preferably 2 to 15 nm. The average primary particle size of the fumed silica (c1) can be measured by observation with an electron microscope.

Further, the specific surface area of the fumed silica (c1) is desirably in the range of 100 to 1000 m ² /g, and preferably in the range of 200 to 500 m ² /g.

As a commercial item of such a fumed silica (c1), "Aerosil RX300" (trade name, average primary particle size 7 nm), "Aerosil RX-200" (trade name, average primary particle size, 7 nm) are mentioned, for example 12nm), "Aerosil RX-380S" (trade name, average primary particle size 5nm), "Aerosil R-976S" (trade name, average primary particle size 7nm), "Aerosil300" (trade name, average primary particle size 7nm) , "Aerosil 200" (trade name, average primary particle size 12 nm) (all of the above are manufactured by Aerosil Corporation of Japan), "HDK H 20" (trade name, average primary particle size 10 nm, manufactured by Wacker Asahi Kasei Silicones Co., Ltd.).

In the case of using fumed silica (c1), from the viewpoints of excellent storage stability of the resist composition, screen printability, and clarity of the resist film, the amount of the used amount is biphenylarane. The solid content of the base epoxy resin (A) is preferably 1 to 50 parts by mass, preferably 5 to 20 parts by mass, based on 100 parts by mass of the solid content.

Barium sulfate (c2) with an average particle size of 0.1 to 1.0 μm

From the viewpoint of stability and clarity of the resist composition, the average particle diameter of barium sulfate (c2) is preferably 0.01 to 1.0 μm, preferably 0.1 to 1.0 μm, and more preferably 0.2 to 0.5 μm.

As such a commercial item of barium sulfate (c2), for example, "Bariace B-20" (manufactured by Sakai Chemical Industry Co., Ltd., trade name, average particle size: 0.03 μm), "Bariace B-30" (Sakai Chemical Co., Ltd.) Industrial Co., Ltd., trade name, average particle size 0.3 μm), “Barium Sulfate PS-07” (Guangxi Xiangzh Co., Ltd., trade name, average particle size 0.74 μm), “Barium Sulfate HF” (Shenzhou Jiaxin Chemical Co., Ltd., trade name, average particle size 0.9 μm). In addition, the average particle diameter of barium sulfate (c2) can be measured using "UPA-EX250" (trade name, the Nikkiso Co., Ltd. make, particle size distribution analyzer by dynamic light scattering method).

In the case of using barium sulfate (c2), the usage amount thereof is desirably 1 to 70 parts by mass based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A) from the viewpoint of screen printability. The mass part is preferably 10 to 40 mass parts.

Talc (c3) with an average particle size of 1.0 to 10 μm

The talc (c3) is a scaly particle having a layered structure, and has an average particle diameter of 1 to 10 μm, preferably an average particle diameter of 2 to 5 μm.

As a commercial item of talc (c3), "Micro Ace SG-95" (trade name, average particle diameter 2.5 micrometers), "Micro Ace P-8" (trade name, average particle diameter 3.3 micrometers) are mentioned, for example. , "Micro Ace P-3" (trade name, average particle size 5μm), "Micro Ace K-1" (trade name, average particle size 8μm) (the above are manufactured by Nippon Talc Corporation), "micro powder talc AHM80" (Liaoning Company made, average particle size 5μm), "Talc AT-1" (Toyo Kasei Co., Ltd., average particle size 6μm), "Simgon" (Japan Talc Co., Ltd., average particle size 8μm), "MISTRON VAPOR" (Nihon Mistron Co., Ltd. manufactured by Kyowa Mining, with an average particle size of 8 μm), “Talc GTA” (manufactured by Kyowa Mining Co., Ltd., with an average particle size of 10 μm). In addition, the average particle diameter of talc (c3) is the particle diameter measured by the laser diffraction method (C250).

In the case of using talc (c3), from the viewpoint of low warpage and flexibility, the compounding amount is desirably 1 based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A). to 70 parts by mass, preferably 15 to 30 parts by mass.

Organic alkoxy compound (D)

The resist composition of this invention can contain an organic alkoxy compound (D) as needed. Examples of the organic alkoxy compound (D) include trimethyl orthoacetate (MOA), trimethyl orthoformate (MOF), triethyl orthoformate, triethyl orthoacetate, and triiso orthoacetate. Propyl ester, dimethoxypropane, etc.

In the case of using the organic alkoxy compound (D), from the viewpoint of being excellent in the storage stability of the resist composition and providing a resist film excellent in screen printability, the amount of its use is the biphenylarane. The solid content of the base epoxy resin (A) is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the solid content.

The resist composition of the present invention may further contain an imidazole-based curing accelerator, a flame retardant, and an organic solvent as necessary.

The imidazole-based curing accelerator is a catalyst-type curing agent, which can accelerate curing by adding a small amount of epoxy resin.

Specific examples of imidazole-based curing accelerators include imidazole (molecular weight: 68.08), 2-methylimidazole (molecular weight: 82.11), 2-ethylimidazole (molecular weight: 96.13), 2-ethyl-4-methylimidazole (molecular weight 110.16), 2-phenylimidazole (molecular weight 144.18), 2-phenylimidazoline (molecular weight 146.19), 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (molecular weight 158.19) ), 4-methylphenylimidazole (molecular weight 158.19), 1-(2-cyanoethyl)-2-ethyl-4-methyl-imidazole (molecular weight 163.22), 1-(2-cyanoethyl) )-2-phenylimidazole (molecular weight 197.24), 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine (molecular weight 219.25), 2,4 -Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine (molecular weight 248.31), 2,4-diamino-6-[2 '-Undecylimidazolyl-(1')]-ethyl-s-triazine (molecular weight 359.51) and the like. Among them, an imidazole-based curing accelerator having a molecular weight of 200 or more is preferable from the viewpoint of the clarity of the resist film, and specifically, 2,4-diamino-6-[2′-methylimidazolyl-(1 )] ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine.

In the case of using an imidazole-based curing accelerator, the amount used is desirably 1 to 20 parts by mass, preferably 5 to 15 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A). range of copies.

As the above-mentioned flame retardant, non-halogen phosphorus-containing compounds, metal hydroxides, and nitrogen-containing compounds can be suitably used from the viewpoints of environment, flame retardancy, and compatibility with epoxy resins.

As the said non-halogen phosphorus-containing compound, non-halogen phosphoric acid ester, condensed phosphoric acid ester, red phosphorus, etc. are mentioned. As said phosphoric acid ester, various phosphoric acid ester compounds are mentioned, Specifically, triphenyl phosphate, tris-xylyl phosphate, triethyl phosphate, tolyl phenyl phosphate, dimethyl phosphate, phosphoric acid are mentioned. 2-ethylhexyl diphenyl ester, dimethyl methyl phosphate, triallyl phosphate, melamine polyphosphate, etc.

As said condensed phosphoric acid ester, resorcinol bis (diphenyl) phosphoric acid ester, 1, 3- phenylene bis (diphenyl phosphoric acid ester), 1, 3- phenylene bis (xylene) are mentioned phosphazene compounds such as phosphonitrile, bisphenol A bis(diphenyl phosphate), phosphonitrilic acid phenyl ester, etc. Examples of commercially available products include trimethyl phosphate (trade name TMP), triethyl phosphate (trade name TEP), tributyl phosphate (trade name TBP), trioctyl phosphate (trade name TOP), Tributoxyethyl phosphate (trade name TBXP), octyl diphenyl phosphate (trade name 41), tricresyl phosphate (trade name TCP), tolyl diphenyl phosphate (trade name CC2P); triphenyl phosphate Ester (trade name TPP), CR-733S, CR-741, CR-747, PX-200 (above, manufactured by Daihachi Chemical Industry Co., Ltd.); Reofos 35, 50, 65, 90, 110, Reofos BAPP, Kronitex TCP, Kronitex TXP, Kronitex CC2P (above, manufactured by Ajinomoto Co., Ltd.); Z-900 (Purakuto, manufactured by Hoyo Chemical Industry Co., Ltd.), etc.

As said metal hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcites, boehmite, etc. are mentioned. The above-mentioned aluminum hydroxide may be an untreated product, or may be surface-treated with a silane coupling agent having a vinyl or epoxy group at the terminal, stearic acid, oleic acid, phosphoric acid ester, or the like. .

Commercially available products of aluminum hydroxide include: Higilite H42M, Higilite H42S, Hgilite H42T, and Higilite H42ST-V manufactured by Showa Denko Corporation; B1403, B1403ST, B1403T manufactured by Nippon Light Metal Corporation; B-30 manufactured by Pakistan Industrial Corporation , B-325, B-316, B-315, B-312, B-309 and B-303, etc.

As magnesium hydroxide, a natural product or a synthetic product may be used, and a surface untreated product may be used, and a silane coupling agent having a vinyl group or epoxy group at the terminal, stearic acid, oleic acid may be used. , phosphate and other surface-treated magnesium hydroxide, etc. Commercially available products of magnesium hydroxide include KISUMA 5A, KISUMA 5B, KISUMA 5E, KISUMA 5J, KISUMA 5P, and KISUMA 5L manufactured by Kyowa Chemical Co., Ltd.; Magnifin H5, Magnifin H7, and Magnifin H10 manufactured by Albemarle Corporation.

As said nitrogen-containing compound, cyanuric acid cyanurate, ammonium polyphosphate, etc. are mentioned.

Among them, from the viewpoint of flame retardancy, a flame retardant having a thermal decomposition temperature of about 400° C. or higher is preferable, and industrially readily available phosphoric acid ester compounds, condensed phosphoric acid esters, magnesium hydroxide, and aluminum hydroxide are suitable.

In the case of using the above-mentioned flame retardant, from the viewpoint of improving flame retardancy, the usage amount thereof is desirably 1 to 50 parts by mass based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A). parts, preferably in the range of 10 to 45 parts by mass.

As the organic solvent, for example, an organic solvent selected from alcohol-based organic solvents, ether-based organic solvents, ketone-based organic solvents, and ester-based organic solvents and having a solubility parameter (SP value) within the range of 9.0 to 15.0 can be suitably used.

Examples of alcohol-based organic solvents include methanol (SP value 14.5), ethanol (SP value 12.7), n-butanol (SP value 11.4), 2-ethoxyethanol (alias: cellosolve (SP value 10.71)) , ethylene glycol monomethyl ether (alias: methyl cellosolve (SP value 11.68)), ethylene glycol monoethyl ether (alias: ethyl cellosolve (SP value 10.5)), ethylene glycol mono-positive Butyl ether (alias: butyl cellosolve (SP value 9.5)), diethylene glycol monoethyl ether (alias: carbitol (SP value 10.2)), diethylene glycol monobutyl ether (alias: butyl carbitol alcohol (SP value 9.5)) and so on.

As the ether-based organic solvent, (poly)ethylene glycol, (poly)ethylene glycol monomethyl ether, (poly)ethylene glycol monoethyl ether, (poly)ethylene glycol monopropyl ether, (Poly)propylene glycol, (poly)propylene glycol monomethyl ether, (poly)propylene glycol monoethyl ether, (poly)propylene glycol monopropyl ether, polyether modified dimethylsiloxane (eg "BYK-345" , "BYK-348", "BYK-377", trade name, made by BYK Japan KK), etc.

Examples of the ketone-based organic solvent include acetone (SP value 9.9), methyl ethyl ketone (SP value 9.3), methyl isobutyl ketone (SP value 8.4), diisobutyl ketone (SP value 7.8), and cyclohexanone (SP value 9.9), isophorone (SP value 9.4), etc.

Examples of the ester-based organic solvent include ethyl acetate (SP value 9.1), n-butyl acetate (SP value 8.5), isobutyl acetate (SP value 8.3), isoamyl acetate (SP value 7.8), acetic acid Methoxypropyl (SP value 9.2), ethylene glycol monomethyl ether acetate [alias: methyl cellosolve acetate (SP value 9.9)], diethylene glycol monobutyl ether acetate (alias: Carbitol acetate] and so on.

other ingredients

The resist composition of the present invention may appropriately contain coloring components, extenders other than the above, other curing accelerators, antioxidants, surface modifiers, rheology control agents, antifoaming agents, surfactants, and antifouling agents as needed , wetting agents and other ingredients.

系颜料、二

嗪系颜料、二酮吡咯并吡咯系颜料等、铝膏、珍珠粉、石墨、MIO等光亮性颜料等。As the coloring component, for example, coloring pigments can be used, and specific examples thereof include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo-based pigments, phthalocyanine-based pigments, and quinacridone-based pigments. Pigments, isoindoline-based pigments, anthracene-based pigments,

pigment, two

Zine pigments, diketopyrrolopyrrole pigments, etc., aluminum paste, pearl powder, graphite, MIO and other bright pigments, etc.

It is preferable to use carbon black and/or a phthalocyanine-based pigment from the viewpoints of being able to be colored in a small amount and the visibility at the time of detection as the coloring component. As a method of mixing these coloring components, a method of directly adding to a resist composition, and a method of mixing with a dispersing agent, dispersing and gelatinizing, and then mixing into the resist composition are exemplified. In addition, when a pigment with a large specific surface area such as carbon black is used, it is desirable to use a large amount of dispersant. As the above-mentioned dispersion method, for example, there is a method of obtaining a dispersion paste using a ball mill, an egg mill, a sand mill, a shaker, or the like, or a powerful pulverizer.

等四苯基硼盐等。Examples of other curing accelerators include: acid anhydrides such as methyl-5-norbornene-2,3-dicarboxylic acid anhydride; organic phosphines such as triphenylphosphine; metal compounds such as tin octoate; phenyl

such as tetraphenyl boron salt, etc.

The resist composition of the present invention can be prepared by compounding a biphenyl aralkyl type epoxy resin (A), an acid anhydride type curing agent (B), an extender pigment (C) and, if necessary, an organic alkoxy compound (D), An imidazole-based curing accelerator, a flame retardant, an organic solvent, and other components are produced using a disperser, a sand mill, a roll mill, a ball mill, or the like. In addition, a dispersion paste of pigment components may be produced in advance, and then the resist composition may be produced.

The viscosity of the resist composition of this invention is 1 Pa.s - 100 Pa.s normally, Preferably it exists in the range of 5 Pa.s or more and less than 30 Pa.s. In addition, the viscosity of a resist composition can be obtained by measuring with a rotational viscometer (for example, E-type viscometer, manufactured by Toki Sangyo Co., Ltd., RE80 type, number of revolutions: 5 rpm, measurement temperature 25°C).

In addition, the viscosity (structural viscosity index R) of the resist composition is 2.0 or more, preferably 2.1, from the viewpoints of sufficiently coating the resist liquid on the substrate and suppressing the flow of the resist pattern while taking into account the pattern accuracy ~10.0. In addition, the said structural viscosity index R is defined by following formula (1).

R=Va/Vb・・・(1)

(wherein, in the formula (1), Va represents the apparent appearance measured at 5 revolutions per minute with an E-type viscometer (trade name, manufactured by Toki Sangyo Co., Ltd., RE80 type) at a temperature of 25° C. The viscosity (Pa·s) and Vb represent the viscosity (Pa·s) measured in the same manner except that the number of revolutions was 50 times/min.

The resist composition of the present invention described above can be applied to a substrate to form a resist film. Specifically, a resist film of a desired pattern can be formed by screen printing using the resist composition of the present invention.

The above-mentioned base material is not particularly limited, and preferable base materials include phenol resin, epoxy resin, polyamide resin, polyimide resin, or a reinforced resin obtained by reinforcing these resins with glass fibers. A laminated base material in which conductive metals such as copper, gold, silver, aluminum, and chromium are covered on a resin surface base material or a glass base material by means of lamination, vapor deposition, or the like. The substrate and the metal film of these base materials may be constituted by a single layer or may be constituted by a plurality of layers. In addition, through or non-through holes may be provided in the substrate. The thickness and shape of these substrates are also not particularly limited.

As a kind of the screen used for the said screen printing, a polyester screen, a composite screen, a metal screen, a nylon screen, etc. are mentioned. In addition, in the case of printing a high-viscosity paste, a high-tension stainless steel mesh can be used. The squeegee for screen printing can be any shape of circle, rectangle, and square. In addition, in order to reduce the angle of attack (the angle between the screen and the squeegee during printing), a grinding squeegee can also be used. For other printing conditions and the like, conventionally known conditions can be appropriately adjusted. In the screen printing method, in order to cope with the high definition of the circuit pattern, it is preferable to use a fine screen, and it is particularly preferable to use a fine screen of about 100 to 400 meshes. The open area of the wire mesh at this time is preferably about 20 to 50%.

The printed resist composition can be dried by heating to form a resist film. The drying conditions can be appropriately determined, for example, depending on the type of the organic solvent used. Usually, for example, the drying temperature is in the range of 50°C to 200°C, preferably 130°C to 190°C, and the drying time is 1 minute to 100 minutes, preferably 20 minutes. ~80 minutes. The heating device is not particularly limited, and for example, a hot-air furnace, an electric furnace, or the like can be used.

The thickness of the obtained resist film is based on the dry film thickness from the viewpoints of preventing peeling due to external impact during the work process, solder heat resistance, and solvent escape from the coating film, and preventing air bubbles from being entrapped during coating. , desirably 5 to 100 μm, preferably 10 to 30 μm. In addition, the resist composition may be divided and applied in a plurality of times. As a coating method at this time, conventionally known wet-on-wet coating such as two coats and one bake, or dry-on-wet coating such as two coats and two bakes can be used. Pack.

Example

Hereinafter, the present invention will be described in more detail by way of production examples, examples, and comparative examples, but the present invention is not limited thereto. "Part" in each example means "mass part", and "%" means "mass %".

Preparation of resist composition

Example 1

In a metal container, thoroughly mix the following components with a mixer: 100 parts of "NC3000-H" (Note 1), 50 parts of "RikacidHF-08" (Note 3), 25 parts of "Kayahard MCD" (Note 5), "Aerosil" 10 copies of "RX-380S" (Note 7), 30 copies of "BariaceB-30" (Note 12), 20 copies of "KISUMA 5J" (Note 20), and 5 copies of "C11Z-A" (Note 21), using three rolls After grinding with a grinder, isophorone was added, and the solid content was adjusted to obtain a resist composition No. 1 having a solid content of 70%.

Examples 2 to 21 and Comparative Examples 1 to 7

Except having adopted the mixing|blending composition shown in Table 1 - Table 3, it carried out similarly to Example 1, and obtained resist composition No.2-No.28.

[Table 1]

[Table 2]

[table 3]

The meanings of (note) in Tables 1 to 3 are as follows.

(Note 1) NC3000-H: trade name, manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin, epoxy value 280 to 300 g/eq.

(Note 2) jER828EL: trade name, manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A epoxy resin, epoxy equivalent of 184 to 194 g/eq.

(Note 3) Rikacid HF-08: Nippon Rika Co., Ltd., trade name, ester of alicyclic carboxylic acid anhydride and polyalkylene glycol.

(Note 4) Rikacid TMEG-100: Nippon Rika Co., Ltd., trade name, ester of aromatic carboxylic acid anhydride and ethylene glycol.

(Note 5) Kayahard MCD: manufactured by Nippon Kayakuyo Co., Ltd., trade name, methyl-5-norbornene-2,3-dicarboxylic acid anhydride.

(Note 6) FL11: manufactured by Mitsubishi Chemical Corporation, trade name, modified aliphatic polyamine, amine value 255-285 mgKOH/g, viscosity 50-100 mPa·s/25°C, solid content 100%.

(Note 7) Aerosil RX-380S: Japan Aerosil Co., Ltd., trade name, fumed silica, average primary particle size 5 nm.

(Note 8) Aerosil R812: Japan Aerosil Co., Ltd., trade name, fumed silica, average primary particle size of 7 nm.

(Note 9) Aerosil R974: Japan Aerosil Co., Ltd., trade name, fumed silica, average primary particle size 12 nm.

(Note 10) Aerosil R972: Japan Aerosil Co., Ltd., trade name, fumed silica, average primary particle size 16 nm.

(Note 11) Aerosil 130: Japan Aerosil Co., Ltd., trade name, fumed silica, average primary particle size 16 nm.

(Note 12) Bariace B-30: Sakai Chemical Industry Co., Ltd., trade name, barium sulfate, average particle size 0.3 μm.

(Note 13) Barium sulfate PS-07: manufactured by Guangxi Xiangzh Co., Ltd., trade name, barium sulfate, average particle size 0.74 μm.

(Note 14) Barifine BF-20: Sakai Chemical Industry Co., Ltd., trade name, barium sulfate, average particle size 0.03 μm.

(Note 15) Micro Ace SG-95: manufactured by Nippon Talc Corporation, trade name, talc, average particle size 2.5 μm.

(Note 16) Micro Ace P-3: manufactured by Nippon Talc Corporation, trade name, talc, average particle size 5 μm.

(Note 17) NANO ACE D-600: manufactured by Nippon Talc Corporation, trade name, talc, average particle size 0.6 μm.

(Note 18) Talc SSS: manufactured by Nippon Talc Corporation, trade name, talc, average particle size 12 μm.

(Note 19) MOA: manufactured by Nippon Chemical Co., Ltd., trade name, trimethyl orthoacetate.

(Note 20) KISUMA 5J: manufactured by Kyowa Chemical Industry Co., Ltd., product name, flame retardant.

(Note 21) C11Z-A: Shikoku Chemical Industry Co., Ltd. product name, curing accelerator.

Evaluation test

The resist compositions No. 1 to No. 28 obtained as described above were subjected to the following evaluation tests. The results are shown in Table 1 to Table 3 together.

Storage stability:

Each resist composition was hermetically stored in a constant temperature chamber at 50°C, and the state after storage for 30 days was evaluated according to the following criteria.

⊚: The state before storage was immediately returned when the coating composition was stirred, and there was no problem.

○: The coating composition settled and a cake layer was observed, but with less than 10 minutes of stirring (using a stirring blade with a diameter of 3 cm at 500 rpm), there was no aggregate and returned to the state before storage.

Δ: The coating composition settled and a cake layer was observed, but the aggregates returned to the state before storage under stirring for 10 to 60 minutes (using a stirring blade with a diameter of 3 cm at 500 rpm).

×: The coating composition settled, a cake layer was observed, and even after stirring (using a stirring blade with a diameter of 3 cm at a rotation speed of 500 rpm) for more than 60 minutes, aggregates remained.

Clarity:

Using a 200-mesh screen printing plate, each resist composition was coated on a copper clad laminate "UPISEL-N" (product name, manufactured by Ube Industries, Ltd., flexible copper clad laminate, copper foil thickness/polyimide) Film thickness = 9 μm/25 μm) in the shape of a 200 μm square basket pattern, screen printing was performed 5 times in a thin line until the dry film thickness was 20 μm, and the 5th pattern coated substrate was dried at 180°C 30 minutes as a test board.

In addition, the blade speed was 200 mm/sec, the angle of attack was 70°, and the blade speed (speed of returning ink by the blade) was 70 mm/sec.

The following "sharpness A", "sharpness B", and "sharpness C" were evaluated for the obtained test plate.

Clarity A:

The accuracy of the pattern shape of each obtained test plate was observed with a microscope, and evaluated according to the following criteria.

⊚: A pattern can be formed so that the length of one side is less than 100 μm±5 μm.

○: A pattern can be formed so that the length of one side is 100 μm±(5 μm or more and less than 10 μm).

Δ: A pattern can be formed so that the length of one side is 100 μm±(10 μm or more and less than 15 μm).

×: The length of one side of the pattern is 100 μm±15 μm or more.

Sharpness B:

In the microscopic observation of the above-mentioned clarity A, the presence or absence of bleeding was evaluated according to the following criteria.

⊚: No bleeding from the pattern shape was observed at all.

○: Bleeding out from the pattern shape was observed in a very small amount, but it was a level with no problem as a product.

△: Bleeding out from the pattern shape was observed, and there was a possibility that a problem such as solder not adhering subsequently occurred.

×: Bleeding from the pattern shape was clearly observed.

Clarity C:

In the preparation of the test plate, the number of times of continuous printing was changed from 5 to 100, and the precision of the pattern shape was observed with a microscope, and evaluated according to the following criteria.

⊚: A pattern can be formed so that the length of one side is less than 100 μm±5 μm.

○: A pattern can be formed so that the length of one side is 100 μm±(5 μm or more and less than 10 μm).

Δ: A pattern can be formed so that the length of one side is 100 μm±(10 μm or more and less than 15 μm).

×: The length of one side of the pattern is 100 μm±15 μm or more.

Flexibility (folding resistance):

Each resist composition No. 1 to No. 20 was coated on UPILEX 25S (manufactured by Ube Kosan Co., Ltd., polyimide film substrate, thickness 25 μm) using a coater to a dry film thickness of 20 μm , and heat-drying was carried out under the conditions of a substrate surface temperature of 180° C. for 60 minutes to prepare a test piece.

The above-mentioned test piece was folded in half, a load of 1 kg was applied, and the folded portion was observed with a microscope. The same test was performed 10 times, and the evaluation was performed according to the following criteria.

⊚: Cracks and peeling of the coating film at the bent portion were not observed at all.

○: Cracks and peeling were observed in the coating film of the primary bending portion.

Δ: Cracks and peeling were observed in the coating film of the folded portion 2 to 4 times.

×: Cracks and peeling occurred in the coating film of the bent portion in all the tests.

Low warpage:

Test pieces were prepared in the same manner as in the above-mentioned flexibility test. Then, the test piece was cut out into a 50 mm×50 mm square in the state with the base material, the warpage of the four corners was measured, the average value was calculated, and the evaluation was performed according to the following criteria.

⊚: Warpage is less than 3 mm.

○: Warpage is 3 mm or more and less than 7 mm.

△: Warpage is 7 mm or more and less than 12 mm.

×: Warpage is 12 mm or more.

Flammability:

Test pieces were prepared in the same manner as in the above-mentioned flexibility test. For each test piece, a vertical burning test based on the UL94 standard was performed. Evaluation is based on UL94 standard. The UL94 standard (Standard No. 94 of Underwriters Laboratories Inc.) is a standard for flammability testing of plastic materials for parts of devices and appliances.

⊚: VTM-0 in the combustion test.

○: VTM-1 in the combustion test.

×: Indicates burnt.

Chemical resistance:

The same test panel used for the sharpness test was immersed in a 10% hydrochloric acid solution, left at 20°C for 15 minutes, washed with water, air-dried, and then conformed to the checkerboard shape (100 pieces of 1 mm in size) described in JIS K 5600. ×1mm checkerboard) for cutting. Then, it tested by the cellophane tape peeling test, and evaluated based on the following criteria.

◎: 100 checkerboards remained, and no edge damage was observed for each checkerboard.

○: 100 checkerboards remained, but edge damage was observed on the checkerboards.

△: The remaining number of checkerboards is 96 or more and 99 or less.

×: The number of remaining checkerboards is 95 or less.

Industrial Applicability

The resist composition of the present invention is excellent in storage stability, and can provide a resist film excellent in screen printability, clarity, low warpage, flexibility, chemical resistance and flame retardancy.

Claims (8)

1. A resist composition comprising: A biphenyl aralkyl type epoxy resin (A) represented by the following general formula (I); An acid anhydride-based curing agent (B), comprising a carboxylic acid anhydride (b1) and a carboxylic acid anhydride modified product (b2); and Extender Pigments (C), The resist composition contains 20 to 100 parts by mass of the acid anhydride-based curing agent (B) and 10 to 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A) 200 parts by mass of the extender pigment (C);

In the formula, n represents the repetition number of 1-10. 2 . The resist composition according to claim 1 , wherein the modified carboxylic acid anhydride (b2) is a reaction product of a carboxylic acid anhydride and (poly)alkylene glycol. 3 . 3 . The resist composition according to claim 1 , wherein the usage ratio (mass ratio) of the carboxylic acid anhydride (b1) and the carboxylic acid anhydride modified product (b2) is based on the total solid content of the two components. 4 . , it is (b1)/(b2)=5/5～1/9. 4 . The resist composition according to claim 1 , wherein the extender pigment (C) contains fumed silica (c1) having an average primary particle diameter of 1 to 20 nm, and the fumed silica The usage-amount of silica (c1) is 1-50 mass parts based on 100 mass parts of solid content of the said biphenyl aralkyl type epoxy resin (A). 5 . The resist composition according to claim 1 , wherein the extender pigment (C) contains barium sulfate (c2) having an average particle diameter of 0.01 to 1.0 μm, and the barium sulfate (c2) The usage-amount is 1-70 mass parts based on 100 mass parts of solid content of the said biphenyl aralkyl type epoxy resin (A). The resist composition according to any one of claims 1 to 5, wherein the extender pigment (C) contains talc (c3) having an average particle diameter of 1.0 to 10 μm, and the amount of the talc (c3) used is It is 1-70 mass parts based on 100 mass parts of solid content of the said biphenyl aralkyl type epoxy resin (A). 7 . The resist composition according to claim 1 , further comprising an organic alkoxy compound (D). 8 . 8 . A resist film comprising the resist composition according to claim 1 .