CN111684011B

CN111684011B - Resist composition and resist film

Info

Publication number: CN111684011B
Application number: CN201980009865.5A
Authority: CN
Inventors: 户塚凉; 大西贤午
Original assignee: Kansai Paint Co Ltd
Current assignee: Kansai Paint Co Ltd
Priority date: 2018-02-08
Filing date: 2019-01-08
Publication date: 2023-09-01
Anticipated expiration: 2039-01-08
Also published as: WO2019155800A1; TWI794394B; JP6563158B1; TW201934655A; JPWO2019155800A1; CN111684011A

Abstract

The invention aims to provide a resist composition which has excellent storage stability and excellent screen printability, 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-based curing agent (B) comprising a carboxylic acid anhydride (B1) and a carboxylic acid anhydride-modified product (B2), and an extender pigment (C); the resist composition contains 20 to 100 parts by mass of the acid anhydride-based 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-based epoxy resin (A).

Description

Resist composition and resist film

Technical Field

The present invention relates to a resist composition and a resist film which are excellent in storage stability, screen printability, sharpness, low warpage, flexibility, chemical resistance and flame retardancy.

Background

The purpose of the solder resist is to prevent the solder from adhering to unnecessary portions and to protect circuits when soldering components to a printed wiring board. Cured films formed from resist compositions used for this purpose are required to satisfy various properties such as adhesion to a substrate, flame retardancy, electrical insulation, solder heat resistance, chemical resistance (solvent resistance, alkali resistance and acid resistance), and plating resistance. In addition, in recent years, there has been an increasing demand for high-definition and flexible circuit boards, and flexibility and low warpage after application and curing are also indispensable.

Conventionally, patterning by a resist composition is generally performed by exposing and etching a photosensitive composition, but a large number of chemical solutions such as a photoresist composition, a developer, an etching solution, and a stripping solution are required, and complicated steps are required. Therefore, there is a demand for forming a high-definition pattern film by screen printing without an exposure process.

In view of this, for example, patent document 1 proposes a resist composition for printing, which contains (a) a biphenyl aralkyl type epoxy resin, (B) at least 1 amine type curing agent having an amine value in the range of 100 to 500mgKOH/g, (C) microsilica having an average primary particle diameter in the range of 1 to 100nm, (D) a flake extender pigment, and (E) an organic solvent, wherein the content of component (D) is 0.1 to 100 parts by mass based on 100 parts by mass of the resin solid component of the epoxy resin (a).

However, in the course of pursuing improvement in performance, the above-mentioned resist composition for printing is insufficient in storage stability, and further, improvement in any performance of screen printability, sharpness, low warpage, flexibility and flame retardancy is required.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2017-82089

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a resist composition which has excellent storage stability, screen printability, sharpness, low warpage, flexibility, chemical resistance and flame retardancy.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a resist composition containing a biphenyl aralkyl type epoxy resin (a), an acid anhydride-based curing agent (B) comprising an alicyclic carboxylic anhydride (B1) and an alicyclic carboxylic anhydride-modified product (B2), and an extender pigment (C) in a specific ratio, and have completed the present invention.

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 pigment (C),

the resist composition contains 20 to 100 parts by mass of the acid anhydride-based 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-based epoxy resin (A);

[ chemical 1]

(wherein n represents a repetition number of 1 to 10).

Effects of the invention

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

Detailed Description

The resist composition of the present invention contains: biphenyl aralkyl type epoxy resins (a); an acid anhydride-based curing agent (B) comprising a carboxylic acid anhydride (B1) and a carboxylic acid anhydride-modified product (B2); and extender pigment (C).

Biphenyl aralkyl type epoxy resin (A)

The biphenyl aralkyl type epoxy resin (a) used in the present invention is generally a multifunctional epoxy resin which is derived from a biphenyl derivative and a compound having a phenol skeleton such as a phenol compound and a naphthol compound and contains 2 or more epoxy groups in the molecule, and is represented by the general formula (I).

[ chemical 2]

(wherein n represents a repetition number of 1 to 10).

The phenol aralkyl type resin as a raw material of the biphenyl aralkyl type epoxy resin (a) can be produced, for example, by a condensation reaction in which a substituted methylenediphenyl compound such as 4,4 '-dimethoxymethyldiphenyl or 4,4' -dihalomethyldiphenyl is condensed with a phenol compound under acidic conditions. Then, the phenol aralkyl resin is reacted with a halogenated epoxide such as epichlorohydrin or β -methyl epichlorohydrin to be glycidylated, whereby the compound of the general formula (I) can be obtained.

Examples of the biphenyl aralkyl type epoxy resin (A) include commercially available products such as "NC-3000", "NC-3000-L", "NC3000-H", "NC3000-FH" and "NC3100" manufactured by Nippon chemical Co., ltd.

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

Anhydride curing agent (B)

The acid anhydride-based curing agent (B) used in the present invention contains a carboxylic acid anhydride (B1) and a modified product (B2) of the carboxylic acid anhydride.

Carboxylic anhydride (b 1)：

Examples of the carboxylic anhydride (b 1) include: anhydrides of alicyclic carboxylic acids such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, chlorobridge anhydride, nadic anhydride (himic anhydride), 5- (2, 5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, chlorobridge acid (chlorobridge acid), and methyl endomethylene tetrahydrophthalic acid; anhydrides of aliphatic carboxylic acids such as dodecenyl succinic anhydride, polyazelaic anhydride, polysebacic anhydride, and polysebacic dianhydride; and anhydrides of aromatic carboxylic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, and biphenyl tetracarboxylic anhydride. As the commercial product of the carboxylic anhydride (b 1), "Kayahard MCD" (methyl-5-norbornene-2, 3-dicarboxylic anhydride) manufactured by Nippon chemical Co., ltd., or "Rikacid HH" (hexahydrophthalic anhydride), "Rikacid MH-T" (methyl hexahydrophthalic anhydride), "Rikacid MH-700" (methyl hexahydrophthalic anhydride) manufactured by Nippon chemical Co., ltd.) may be used.

Modification of carboxylic anhydride (b 2)：

Examples of the modified carboxylic anhydride (b 2) include: a modified product of an alicyclic carboxylic acid anhydride, a modified product of an aliphatic carboxylic acid anhydride, and a modified product of an aromatic carboxylic acid anhydride. Specifically, there may be mentioned: esters of alicyclic carboxylic anhydrides with (poly) alkylene glycols, esters of aliphatic carboxylic anhydrides with (poly) alkylene glycols, esters of aromatic carboxylic anhydride modifications with (poly) alkylene glycols, and the like. Examples of the (poly) alkylene glycol include: ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, blocks of polyethylene glycol and polypropylene glycol, and the like. As the commercial products of the modified product (b 2) of the carboxylic anhydride, "Rikacid HF-08" (ester of alicyclic carboxylic anhydride with (poly) alkylene glycol) and "Rikacid TMEG-100" (ester of aromatic carboxylic anhydride with ethylene glycol) manufactured by New Japan physical and chemical Co., ltd.) and the like can be used.

In the acid anhydride-based curing agent (B), the use ratio (mass ratio) of the carboxylic anhydride (B1) to the carboxylic anhydride-modified material (B2) is preferably from 4/6 to 2/8 based on the total of the solid components of the two components, from the viewpoints of curability, flexibility and chemical resistance.

The amount of the acid anhydride-based curing agent (B) used is 20 to 100 parts by mass, preferably 40 to 90 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl-based epoxy resin (a) from the viewpoints of curability, flexibility, chemical resistance and flame retardancy.

Extender pigment (C)

The extender pigment (C) used in the present invention includes: clay, silica, fumed silica, barium sulfate, talc, calcium carbonate, white carbon, diatomaceous earth, aluminum magnesium carbonate flakes, mica flakes, and the like.

The amount of the extender pigment (C) used is 10 to 200 parts by mass, preferably 30 to 180 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (a) from the viewpoints of storage stability, low warpage, flexibility, chemical resistance and flame retardance.

In the present invention, from the viewpoints of improving storage stability, low warpage, flexibility, chemical resistance and flame retardancy, it is particularly desirable to contain fumed silica (C1), barium sulfate (C2) and talc (C3) as the extender pigment (C) as described below.

Fumed silica (c 1) having an average primary particle diameter of 1 to 20nm

The fumed silica (c 1) is amorphous, glassy and spherical, non-porous silica synthesized by gasifying silicon chloride and by a vapor phase reaction in a high Wen Qingyan, and has an average primary particle diameter of 1 to 20nm, preferably 2 to 15nm. The average primary particle diameter of the fumed silica (c 1) can be measured by an observation electron microscope.

Further, the specific surface area of the fumed silica (c 1) is desirably 100 to 1000m ² Preferably 200 to 500m ² The range of/g.

Examples of commercial products of such fumed silica (c 1) include: "Aerosil RX300" (trade name, average primary particle size 7 nm), "Aerosil RX-200" (trade name, average primary particle size 12 nm), "Aerosil RX-380S" (trade name, average primary particle size 5 nm), "Aerosil R-976S" (trade name, average primary particle size 7 nm), "Aerosil300" (trade name, average primary particle size 7 nm), "Aerosil 200" (trade name, average primary particle size 12 nm) (all of which are manufactured by Japanese Aerosil Co., ltd.), and "HDK H20" (trade name, average primary particle size 10nm, manufactured by Wakexu chemical silicone Co., ltd.) etc.

When the fumed silica (c 1) is used, the amount of the fumed silica (c 1) to be used is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (a), from the viewpoints of excellent storage stability of the resist composition, screen printability and sharpness of the resist film.

Barium sulfate (c 2) having an average particle diameter of 0.1 to 1.0 μm

The average particle diameter of barium sulfate (c 2) is preferably 0.01 to 1.0. Mu.m, more preferably 0.1 to 1.0. Mu.m, and still more preferably 0.2 to 0.5. Mu.m, from the viewpoints of stability and sharpness of the resist composition.

Examples of commercial products of such barium sulfate (c 2) include: "Bariace B-20" (trade name, average particle size 0.03 μm, manufactured by Sakai chemical industry Co., ltd.), "Bariace B-30" (trade name, average particle size 0.3 μm, manufactured by Saku chemical industry Co., ltd.), "barium sulfate PS-07" (trade name, average particle size 0.74 μm, manufactured by Guangxi Xingzh chemical Co., ltd.), "barium sulfate HF" (trade name, average particle size 0.9 μm, manufactured by Shenzhou Jia Xin chemical Co., ltd.). The average particle diameter of barium sulfate (c 2) can be measured by using "UPA-EX250" (trade name, manufactured by Nikkin corporation, particle size distribution measuring apparatus by dynamic light scattering method).

In the case of using barium sulfate (c 2), the amount is desirably 1 to 70 parts by mass, preferably 10 to 40 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.

Talc (c 3) having an average particle diameter of 1.0 to 10 μm

The talc (c 3) is a scaly particle having a layered structure, and has an average particle diameter of 1 to 10. Mu.m, preferably 2 to 5. Mu.m.

Examples of commercial products of talc (c 3) include: "MicroAce SG-95" (trade name, average particle size 2.5 μm), "MicroAce P-8" (trade name, average particle size 3.3 μm), "MicroAce P-3" (trade name, average particle size 5 μm), "MicroAce K-1" (trade name, average particle size 8 μm) (above is made by Japanese talc Co., ltd.), "micropowder talc AHM80" (made by Liaoning Co., average particle size 5 μm), "talc AT-1" (made by Toyo Cheng Co., ltd.), "Simgon" (made by Japanese talc Co., average particle size 8 μm), "MISTRON VAPOR" (made by Nihon Mistron Co., ltd., "talc GTA" (made by Co., ltd., average particle size 10 μm), etc. The average particle diameter of talc (C3) is the particle diameter measured by the laser diffraction method (C250).

In the case of using talc (c 3), the amount is preferably 1 to 70 parts by mass, and more preferably 15 to 30 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (a), from the viewpoints of low warpage and flexibility.

Organic alkoxy Compound (D)

The resist composition of the invention may contain an organic alkoxy compound (D) as required. Examples of the organic alkoxy compound (D) include: trimethyl orthoacetate (MOA), trimethyl orthoformate (MOF), triethyl orthoformate, triethyl orthoacetate, triisopropyl orthoacetate, dimethoxypropane, etc.

When the organic alkoxy compound (D) is used, the amount thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (a), from the viewpoint that the resist composition is excellent in storage stability and a resist film excellent in screen printability can be provided.

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

The imidazole curing accelerator is a catalyst type curing agent, and curing can be accelerated by adding a small amount of the imidazole curing accelerator to the epoxy resin.

Specific examples of the imidazole-based curing accelerator 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' -methylimidazole- (1 ') ] ethyl-s-triazine (molecular weight 219.25), 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazole- (1 ') ] -ethyl-s-triazine (molecular weight 248.31), 2, 4-diamino-6- [2' -undecylimidazole- (1 ') ] -ethyl-s-triazine (molecular weight 359.51), and the like. Among them, from the viewpoint of the clarity of the resist film, imidazole-based curing accelerators having a molecular weight of 200 or more are preferable, and specifically, 2, 4-diamino-6- [2 '-methylimidazolyl- (1) ] ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 '-methylimidazolyl- (1') ] -ethyl-s-triazine, and 2, 4-diamino-6- [2 '-undecylimidazolyl- (1') ] -ethyl-s-triazine are particularly preferable.

When the imidazole-based curing accelerator is used, the amount is preferably in the range of 1 to 20 parts by mass, and more preferably 5 to 15 parts by mass, based on 100 parts by mass of the solid content of the biphenyl aralkyl-based epoxy resin (a).

As the above flame retardant, a non-halogen phosphorus-containing compound, a metal hydroxide and a nitrogen-containing compound can be suitably used from the viewpoints of environment, flame retardancy and compatibility with an epoxy resin.

Examples of the non-halogen phosphorus-containing compound include: non-halogen phosphates, condensed phosphates, red phosphorus, and the like. The above-mentioned phosphoric acid ester may be various phosphoric acid ester compounds, and specifically, may be: triphenyl phosphate, tri-xylene phosphate, triethyl phosphate, tolyl phenyl phosphate, xylene phosphate, 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate, triallyl phosphate, melamine polyphosphate, and the like.

Examples of the condensed phosphoric ester include: phosphazene compounds such as resorcinol bis (diphenyl) phosphate, 1, 3-phenylene bis (diphenyl phosphate), 1, 3-phenylene bis (xylyl) phosphate, bisphenol A bis (diphenyl phosphate), and phosphazene phenyl ester (phosphonitrilic acid phenyl ester). Examples of commercial 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), cresyl diphenyl phosphate (trade name CC 2P); triphenyl phosphate (trade name: TPP), CR-733, S, CR-741, CR-747, PX-200 (above, manufactured by Daba chemical Co., ltd.); reofos 35, 50, 65, 90, 110, reofos BAPP, kronitx TCP, kronitx TXP, kronitx CC2P (manufactured by the above, sambucus corporation); z-900 (a case コ, manufactured by the International chemical industry Co., ltd.).

The metal hydroxide may be: aluminum hydroxide, magnesium hydroxide, hydrotalcite, boehmite, and the like. The aluminum hydroxide may be a surface-untreated product, or may be used, for example, aluminum hydroxide surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the end, stearic acid, oleic acid, phosphate ester, or the like.

Examples of commercial products of aluminum hydroxide include: higilite H42M, higilite H42S, higilite H42T, higilite H42ST-V manufactured by Showa electric company; b1403, B1403ST, B1403T manufactured by japan light metals company; b-30, B-325, B-316, B-315, B-312, B-309, and B-303 manufactured by Bass industries, ltd.

The magnesium hydroxide may be a natural product or a synthetic product, or may be a surface-untreated product, or may be magnesium hydroxide surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the end, stearic acid, oleic acid, phosphate ester, or the like. Examples of the commercial product of magnesium hydroxide include: KISUMA 5A, KISUMA 5B, KISUMA 5E, KISUMA 5J, KISUMA 5P, KISUMA 5L, manufactured by synergistic chemistry; magnifin H5, magnifin H7, magnifin H10, etc. manufactured by Albemarle corporation.

Examples of the nitrogen-containing compound include cyanuric acid ester and ammonium polyphosphate.

Among them, from the viewpoint of flame retardancy, flame retardants having a thermal decomposition temperature of about 400 ℃ or higher are preferable, and phosphate compounds, condensed phosphates, magnesium hydroxide, and aluminum hydroxide, which are industrially easily available, are suitable.

In the case of using the above flame retardant, the amount is preferably in the range of 1 to 50 parts by mass, and more preferably 10 to 45 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 improving the flame retardancy.

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

Examples of the alcohol-based organic solvent 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-n-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 (SP value 9.5)), and the like.

Examples of the ether-based organic solvent include: (Poly) ethylene glycol, (Poly) ethylene glycol monomethyl ether, (Poly) ethylene glycol monoethyl ether, (Poly) ethylene glycol monopropyl ether, (Poly) propylene glycol monomethyl ether, (Poly) propylene glycol monoethyl ether, (Poly) propylene glycol monopropyl ether, polyether modified dimethylsiloxane (e.g., "BYK-345", "BYK-348", "BYK-377", trade name, manufactured by BYK Japan KK) and the like.

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), cyclohexanone (SP value 9.9), isophorone (SP value 9.4), and the like.

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), methoxypropyl acetate (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 the like.

Other ingredients

The resist composition of the present invention may contain other components such as coloring components, extender pigments other than those described above, other curing accelerators, antioxidants, surface regulators, rheology control agents, defoamers, surfactants, antifouling agents, wetting agents, and the like as appropriate.

As the coloring component, for example, a coloring pigment can be used, and specific examples include: titanium oxide, zinc white, carbon black, molybdenum red, prussian blue, cobalt blue, azo-based pigments, phthalocyanine-based pigments, quinacridone-based pigments, isoindoline-based pigments, anthracene-based pigments, and the like,Pigment system, di->Oxazine pigments, diketopyrrolopyrrole pigments, aluminum pastes, pearl powders, graphite, and bright pigments such as MIO.

The coloring component is preferably carbon black and/or a phthalocyanine pigment from the viewpoint of being capable of coloring in a small amount and visibility at the time of detection. Examples of the method of blending these coloring components include: a method of adding directly to a resist composition; and a method of mixing the dispersion paste with a dispersant and then blending the dispersion paste into a resist composition. In addition, when a pigment having a large specific surface area such as carbon black is used, it is desirable to use a large amount of dispersant. Examples of the dispersing method include: a method of obtaining a dispersion paste using a ball mill, an egg mill, a sand mill, a vibrator, or the like, or a powerful pulverizing machine.

Examples of the other curing accelerator include: anhydrides such as methyl-5-norbornene-2, 3-dicarboxylic anhydride; organic phosphines such as triphenylphosphine; metal compounds such as tin octoate; tetraphenyl borateAnd tetraphenylboron salts.

The resist composition of the present invention can be produced by blending the biphenyl aralkyl type epoxy resin (a), the acid anhydride type curing agent (B), the extender pigment (C), and if necessary, the organic alkoxy compound (D), the imidazole type curing accelerator, the flame retardant, the organic solvent, and other components, and using a dispersing machine, a sand mill, a roll mill, a ball mill, and the like. Further, a dispersion paste of pigment components may be prepared in advance, and then a resist composition may be prepared.

The viscosity of the resist composition of the present invention is usually 1pa·s to 100pa·s, preferably in the range of 5pa·s or more and less than 30pa·s. The viscosity of the resist composition can be obtained by measuring with a rotational viscometer (for example, an E-type viscometer, manufactured by Tokyo Co., ltd., RE80 type, rotation speed: 5rpm, measurement temperature 25 ℃), for example.

The viscosity (structural viscosity index R) of the resist composition is 2.0 or more, preferably 2.1 to 10.0, from the viewpoint of being able to sufficiently coat the substrate with the resist liquid and suppressing the flow of the resist pattern while achieving pattern accuracy. The structural viscosity index R is defined by the following formula (1).

R＝Va/Vb·····(1)

(wherein in the formula (1), va represents an apparent viscosity (Pa.s) measured at a rotation number of 5 times/min by an E-type viscometer (trade name, RE80 type manufactured by Tokyo industries, ltd.) at a temperature of 25 ℃ and Vb represents a viscosity (Pa.s) measured by the same operation except that the rotation number is 50 times/min).

The resist composition of the present invention described above may be coated on a substrate to form a resist film. Specifically, screen printing can be performed using the resist composition of the present invention to form a resist film of a desired pattern.

The substrate is not particularly limited, and preferable substrates include: a laminate substrate obtained by laminating or vapor depositing a conductive metal such as copper, gold, silver, aluminum, or chromium on a resin surface substrate such as a phenol resin, an epoxy resin, a polyamide resin, a polyimide resin, or a reinforced resin obtained by reinforcing these resins with glass fibers, or a glass substrate. The substrate and the metal film of these substrates may be formed of a single layer or may be formed of a plurality of layers. Further, a through or non-through hole may be provided in the base material. The thickness and shape of these substrates are not particularly limited either.

As a kind of screen printing plate used for the screen printing, there may be mentioned: polyester wire mesh, combination wire mesh, nylon wire mesh, and the like. In addition, in the case of printing a paste of high viscosity, a stainless steel screen of high tension may be used. The squeegee for screen printing may be any of a circular shape, a rectangular shape, and a square shape, and a polishing squeegee may be used in order to reduce the attack angle (the angle between the screen and the squeegee at the time of printing). For other printing conditions, the conventionally known conditions can be appropriately adjusted. In the screen printing method, in order to cope with the high definition of the circuit pattern, a fine screen is preferably used, and a fine screen of about 100 to 400 mesh is particularly preferably used. The open area of the screen at this time is preferably about 20 to 50%.

The printed resist composition may be dried by heating to form a resist film. The drying conditions can be appropriately determined depending on the kind of the organic solvent used, and generally, for example, the drying temperature is 50 to 200 ℃, preferably 130 to 190 ℃, and the drying time is 1 to 100 minutes, preferably 20 to 80 minutes. The heating device is not particularly limited, and for example, a hot blast stove, an electric stove, or the like can be used.

The thickness of the resulting resist film is preferably 5 to 100 μm, more preferably 10 to 30 μm in terms of dry film thickness, from the viewpoints of preventing peeling accompanying external impact, solder heat resistance, and solvent escape in the coating film during the working process, and preventing inclusion of bubbles during the coating. In addition, the resist composition may be applied in a plurality of times. As a coating method in this case, conventionally known wet-on-wet (wet-on-wet) coating such as two-coat and one-bake, or dry-on-wet (dry-on-wet) coating such as two-coat and two-bake can be used.

Examples

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

Preparation of resist compositionActing as

Example 1

In a metal vessel, the following ingredients were thoroughly mixed by a stirrer: 100 parts of "NC3000-H" (note 1), "Rikacid HF-08" (note 3), "Kayahard MCD" (note 5), "25 parts of" Aerosil RX-380S "(note 7)," 10 parts of "Bariace B-30" (note 12), "30 parts of" KISUMA 5J "(note 20)," 20 parts of "C11Z-A" (note 21) 5 parts of "were milled using a three-roll mill, and isophorone was added thereto to adjust the solid content, thereby obtaining a resist composition No.1 having a solid content of 70%.

Examples 2 to 21 and comparative examples 1 to 7

Resist compositions No.2 to No.28 were obtained in the same manner as in example 1 except that the compounding ratios shown in tables 1 to 3 were used.

TABLE 1

TABLE 2

TABLE 3

The meanings of (notes) in tables 1 to 3 are as follows.

(note 1) NC3000-H: the product name is biphenyl aralkyl type epoxy resin manufactured by Japanese chemical Co., ltd, and the epoxy value is 280-300 g/eq.

(note 2) jER828EL: trade name, bisphenol A type epoxy resin manufactured by Mitsubishi chemical corporation, epoxy equivalent 184 to 194g/eq.

(note 3) Rikacid HF-08: new Japan chemical Co., ltd., trade name, esters of alicyclic carboxylic acid anhydrides and polyalkylene glycols.

(Note 4) Rikacid TMEG-100: new Kagaku Kogyo Co., ltd., trade name, an ester of an aromatic carboxylic acid anhydride with ethylene glycol.

(note 5) Kayahard MCD: manufactured by japan chemical society, trade name, methyl-5-norbornene-2, 3-dicarboxylic anhydride.

(note 6) FL11: trade name, modified aliphatic polyamine, amine value 255-285 mgKOH/g, viscosity 50-100 mPa.s/25 ℃ and solid content 100%.

(note 7) Aerosil RX-380S: japanese Aerosil Co., ltd., trade name, fumed silica, average primary particle diameter 5nm.

(note 8) Aerosil R812: japanese Aerosil Co., ltd., trade name, fumed silica, average primary particle diameter of 7nm.

(note 9) Aerosil R974: the average primary particle diameter of fumed silica is 12nm, trade name of Japanese Aerosil Co., ltd.

(note 10) Aerosil R972: the average primary particle diameter of fumed silica is 16nm, trade name of Japanese Aerosil Co., ltd.

(note 11) Aerosil 130: the average primary particle diameter of fumed silica is 16nm, trade name of Japanese Aerosil Co., ltd.

(note 12) Bariace B-30: sakukukuai chemical Co., ltd., trade name, barium sulfate, and an average particle diameter of 0.3 μm.

(note 13) barium sulfate PS-07: manufactured by Guangxi Xiangazh company, trade name, barium sulfate, and average particle diameter of 0.74 μm.

(note 14) Barifine BF-20: sakukukuai chemical Co., ltd., trade name, barium sulfate, and an average particle diameter of 0.03 μm.

(Note 15) Micro Ace SG-95: talc, trade name, average particle size 2.5 μm, manufactured by Japanese talc Co., ltd.

(Note 16) MicroAce P-3: talc, trade name, average particle size 5 μm, manufactured by Japanese talc Co., ltd.

(note 17) NANO ACE D-600: talc, trade name, average particle size 0.6 μm, manufactured by Japanese talc Co., ltd.

(note 18) talc SSS: talc, trade name, average particle size 12 μm, manufactured by Japanese talc Co., ltd.

(note 19) MOA: nibao chemical Co., ltd., trade name, trimethyl orthoacetate.

(note 20) KISUMA 5J: manufactured by the company chemical industry, product name, flame retardant.

(note 21) C11Z-a: the curing accelerator is manufactured by Kagaku Kogyo Co., ltd.

Evaluation test

The resist compositions No.1 to No.28 prepared as described above were supplied to the following evaluation test. The results are shown in tables 1 to 3.

Storage stability:

each resist composition was stored in a sealed state in a thermostatic chamber at 50℃and the state after 30 days of storage was evaluated according to the following criteria.

And (3) the following materials: the coating composition returns to the state immediately before storage when stirred, and is free of problems.

O: the coating composition settled and a cake layer was observed, but no aggregates were returned to the state before storage with stirring for less than 10 minutes (using stirring blades of 3cm diameter at 500 rpm).

Delta: 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 stirring blades having a diameter of 3cm at a rotation speed of 500 rpm).

X: the coating composition settled and a cake layer was observed, and aggregates remained even if stirred (using stirring blades of 3cm diameter at 500 rpm) for more than 60 minutes.

Definition:

using a 200-mesh screen printing plate, each resist composition was formed into a 200 μm square basket-like pattern shape on a copper-clad laminate "UPISEL-N" (product name, manufactured by Yu Xingzhi Co., ltd., flexible copper-clad laminate, copper foil thickness/polyimide film thickness=9 μm/25 μm), followed by 5 continuous screen printing in a fine line to a dry film thickness of 20 μm, and the 5 th pattern-coated substrate was dried at 180℃for 30 minutes to obtain a test plate.

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

The test panels obtained were evaluated for "clarity a", "clarity B", and "clarity C" as follows.

Definition a:

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

And (3) the following materials: the pattern may be formed with a length of one side less than 100 μm + -5 μm.

O: the pattern may be formed with a length of one side of 100 μm± (5 μm or more and less than 10 μm).

Delta: the pattern may be formed with a length of one side of 100 μm± (10 μm or more and less than 15 μm).

X: the length of one side of the pattern is more than 100 mu m + -15 mu m.

Definition B:

in the microscopic observation of the above definition a, the presence or absence of bleeding was evaluated according to the following criteria.

And (3) the following materials: no exudation from the pattern shape was observed at all.

O: a very small amount of bleeding from the pattern shape was observed, but as a product, there was no problem level.

Delta: exudation from the pattern shape was observed, and then, defects such as solder non-attachment were likely to occur.

X: exudation from the pattern shape was clearly observed.

Definition C:

in the production of the test board, the number of continuous printing was changed from 5 to 100, and the accuracy of pattern shape was observed with a microscope, and evaluated according to the following criteria.

X: the length of one side of the pattern is more than 100 mu m + -15 mu m.

Flexibility (folding endurance):

each of the resist compositions No.1 to No.20 was coated with a coating machine to a dry film thickness of 20 μm on UPILEX 25S (manufactured by Yu Xingzhi Co., ltd., thickness of 25 μm) and dried by heating at a substrate surface temperature of 180℃for 60 minutes to prepare test pieces.

The test piece was folded in half, a load of 1kg 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.

And (3) the following materials: no cracks and peeling of the coating film at the bent portion were observed at a time.

O: cracks and peeling of the coating film at the 1-fold bend were observed.

Delta: cracks and peeling of the coating film at the bent portion of 2 to 4 times were observed.

X: in all the tests, the coating film at the bent portion was cracked and peeled off.

Low warpage:

test pieces were produced in the same manner as in the above-described flexibility test. Then, the test piece was cut out to 50mm×50mm square with the base material, and the warpage at 4 corners was measured, and the average value was calculated and evaluated according to the following criteria.

And (3) the following materials: the warpage is less than 3mm.

O: the warpage is 3mm or more and less than 7mm.

Delta: the warpage is 7mm or more and less than 12mm.

X: the warp is more than 12mm.

Combustibility:

test pieces were produced in the same manner as in the above-described flexibility test. For each test piece, a vertical combustion test based on UL94 standard was performed. Evaluation was performed based on UL94 standards. UL94 standard (standard number 94 of Underwriters Laboratories inc.) is a standard for the flammability test of plastic materials for devices and appliance parts.

And (3) the following materials: VTM-0 in the burn test.

O: VTM-1 in the burn test.

X: indicating that it is burned.

Chemical resistance:

the same test plate as used for the clarity test was immersed in a 10% hydrochloric acid solution, left at 20℃for 15 minutes, washed with water, air-dried, and cut according to the checkerboard shape described in JIS K5600 (100 checkerboards having dimensions of 1 mm. Times.1 mm). Then, the test was performed by a cellophane tape peeling test, and the evaluation was performed according to the following criteria.

And (3) the following materials: 100 checkerboards remained, with no edge damage observed for each checkerboard.

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

Delta: the number of residues in the checkerboard is 96 to 99 inclusive.

X: the number of residues in the checkerboard is 95 or less.

Industrial applicability

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

Claims

1. A resist composition comprising:

extender pigment (C),

the carboxylic anhydride-modified material (b 2) is a reaction product of a carboxylic anhydride and a polyalkylene glycol or an alkylene glycol,

wherein n represents a repetition number of 1 to 10.

2. The resist composition according to claim 1, wherein the ratio of the carboxylic anhydride (b 1) to the carboxylic anhydride-modified compound (b 2) is (b 1)/(b 2) =5/5 to 1/9 in terms of the total of the solid components of the two components by mass ratio.

3. The resist composition according to claim 1 or 2, wherein the extender pigment (C) comprises fumed silica (C1) having an average primary particle diameter of 1 to 20nm, and the fumed silica (C1) is used in an amount of 1 to 50 parts by mass based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A).

4. The resist composition according to claim 1 or 2, wherein the extender pigment (C) comprises barium sulfate (C2) having an average particle diameter of 0.01 to 1.0 μm, and the amount of the barium sulfate (C2) used is 1 to 70 parts by mass based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A).

5. The resist composition according to claim 1 or 2, wherein the extender pigment (C) comprises talc (C3) having an average particle diameter of 1.0 to 10 μm, and the talc (C3) is used in an amount of 1 to 70 parts by mass based on 100 parts by mass of the solid content of the biphenyl aralkyl type epoxy resin (A).

6. The resist composition according to claim 1 or 2, further comprising an organic alkoxy compound (D).

7. A resist film comprising the resist composition according to any one of claims 1 to 6.