JP2003183401A - Curable resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition capable of preventing trouble caused by electrostatic charge and suppressing production costs while keeping physical properties required for a printed circuit board, and further giving good preserving stability to the resist ink after formulating a curing agent. <P>SOLUTION: This curable resin composition comprises curable components such as a polycarboxylic acid having two or more carboxy groups in the molecule and an epoxy resin, a curing agent and an electroconductive filler (carbon black, etc.), having pH higher than 7.0. The cured product of the composition is also provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition for a protective coating used for a solder resist of a printed wiring board, a cured product thereof, a printed wiring board coated with the cured product, and the curable resin. The present invention relates to a method for producing a composition.

[0002]

2. Description of the Related Art A printed wiring board is a polyimide film
Film, phenol resin laminated board, glass epoxy resin coated board
Substrate such as, copper foil and acrylic epoxy forming circuit
It consists of a resist protective film mainly composed of
Has been. Of these, the substrate and the resist protective film are originally
Since it is used for insulation, it has high insulation properties.
ing. For example, the resist used in printed wiring boards
The coating has a surface resistance of 10 ¹²With insulation resistance of Ω or more
There is. Due to this high insulation, these materials are easily charged
It has a property.

On the other hand, in recent years, with the progress of miniaturization and high performance of electronic devices, the occurrence of product defects due to static electricity at the time of manufacture has been regarded as a problem, and static electricity antistatic technology has been emphasized. For example, in the manufacturing process of electronic devices, a method of using an electrically conductive material such as antistatic clothing and a wrist strap, or a method of supplying an electric charge such as an ionizer is used to prevent the electrostatic charge. However, there are increasing cases in which the antistatic property is not sufficient only by the above measures, and as a countermeasure, attempts have been made to provide a printed wiring board protected by a resist film with an antistatic function. For example, Japanese Patent Laid-Open No. 02-17
Japanese Patent No. 4289 and Japanese Patent Application Laid-Open No. 04-261539 propose to print an antistatic ink containing conductive polymer particles and metal oxides on the upper surface or the upper and lower surfaces of a resist film of a printed wiring board.

[0004]

The method of forming a conductive film on the surface of a resist film as described above complicates the manufacturing process and causes an increase in cost. Further, when the conductive coating is formed, the terminal portion of the circuit pattern, which should not be coated originally, may be coated, resulting in contact failure. Furthermore, the antistatic agent such as a surfactant contained in the conductive film has a low melting point, insufficient chemical resistance and heat resistance, and is more likely to exude from the resist layer. There are many. For this reason, troubles may occur due to the vaporized substances, exuded substances on the surface of the resist coating, and their deteriorated substances adhering to the electronic components in the drying step after the application of the resist ink.

Conventionally, it has been practiced to add a conductive inorganic substance such as metal powder or carbon black to a resin for the purpose of preventing static electricity. However, there is no example in which this antistatic method is applied to the resist ink itself used for the electronic substrate material. In addition, merely adding a general conductive inorganic substance for the purpose of antistatic cannot sufficiently obtain the properties required for the resist ink, and in some cases, it may be adversely affected.

Conventional resist inks, particularly resist inks containing a carboxyl group, are not
When stored at room temperature, there is a problem that gel cannot be used for a short period of time because gel is generated in the ink due to a thermal crosslinking reaction. Therefore, it is difficult to store it at room temperature for a long period of time, and it is common to store it at low temperature or store the main component such as curable resin and the curing component such as curing catalyst separately and mix them just before use. ing. However, in the case of low temperature storage, a freezer and a refrigerator are required, and it is necessary to return the temperature to room temperature for a long time before use. Also, the shelf life of the mixture is not sufficient when stored in the refrigerator. When the main component and the curing component are separated, the life of the ink becomes longer, but the process of mixing the ink is required, which increases the number of work steps and increases the manufacturing cost. Depending on the types of the main agent and the curing agent, problems such as insufficient dispersion cannot be obtained by mixing before use, and there are many restrictions on the use of the main agent and curing agent components that can be used.

An object of the present invention is to solve the above-mentioned problems of the prior art in a printed wiring board. That is, while maintaining the physical properties required for the printed circuit board, it prevents troubles due to electrostatic charging, suppresses the manufacturing cost, and has good storage stability of the resist ink after the curing agent is mixed. An object is to provide a resin composition.

[0008]

Means for Solving the Problems As a result of sincere research for solving the above-mentioned problems, the present inventors have found that the polycarboxylic acid resin having two or more carboxyl groups in the molecule has
A one-component printed wiring board ink having excellent storage stability can be obtained from a curable resin composition containing a conductive filler of more than 7.0, and the cured product has a surface resistance of 1
It has been found that not only does it have a stable antistatic property for a long period of time in the range of 0 ³ to 10 ¹¹ Ω, but it is also excellent in properties such as plating resistance, chemical resistance, high heat resistance, flexibility, etc. Has been completed. That is, the present invention relates to a curable resin composition shown in the following [1] to [15], a cured product thereof, a printed wiring board, and a method for producing the curable resin composition.

[1] A polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule, a curing component (B), a curing agent (C) and a conductive filler (D) having a pH of more than 7.0. And a curable resin composition. [2] An epoxy (meth) acrylate resin or urethane (meth) acrylate resin in which a polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule has two or more carboxyl groups in one molecule. The curable resin composition according to [1].

[3] The curable resin composition as described in [2], which contains a photopolymerization initiator (E). [4] A diluent (F) is included in [1] to
The curable resin composition according to any one of [3].

[5] The acid value of the polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule is 5 to 1
50 mgKOH / g and weight average molecular weight of 100
0 to 100,000 [1]
The curable resin composition according to any one of [4]. [6] The curable resin composition according to any one of [1] to [5], wherein the curing component (B) is an epoxy resin having two or more epoxy groups in one molecule. . [7] The curable resin composition according to any one of [1] to [6], wherein the conductive filler (D) is carbon black.

[8] Viscosity is 500 to 500,000 m
Pa · s, The curable resin composition according to any one of [1] to [7]. [9] A cured product obtained by curing the curable resin composition according to any one of [1] to [8]. [10] The cured product according to [9], which has a surface resistance of 10 ³ to 10 ¹¹ Ω.

[11] A resist ink containing the curable resin composition according to any one of [1] to [9]. [12] A solder resist comprising the cured product according to [9] or [10]. [13] A protective film made of the cured product according to [9] or [10]. [14] A printed wiring board partially or entirely coated with the cured product [[9] or [10].

[15] The pH of the polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule is 7.
Step (I) of mixing more than 0 conductive filler (D)
And a polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule in the mixture obtained in the step (I),
Step (II) of mixing the curing component (B), the curing agent (C) and, if necessary, the photopolymerization initiator (E) and the diluent (F)
A method for producing a curable resin composition comprising: [16] Conductive filler (D) having a pH of more than 7.0
A method for preventing electrification of a resist ink, which comprises adding

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule of the present invention (hereinafter, may be simply referred to as “polycarboxylic acid resin (A)” or “component (A)”). , A resin having a chemically bonded carboxyl group in the resin molecule. Any known and commonly used polycarboxylic acid resin can be used as long as it has two or more carboxyl groups in one molecule. For example, epoxy (meth) acrylate resin having a carboxyl group, urethane (meth) acrylate resin, polystyrene resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polyester resin or the like can be used. Here, "(meth) acrylate" means methacrylate or acrylate. Among these, polycarboxylic acid resins having a photopolymerizable unsaturated bond in one molecule are preferable. Specific examples include epoxy (meth) acrylate resins and urethane (meth) acrylate resins having two or more carboxyl groups in the molecule.

The epoxy (meth) acrylate resin having two or more carboxyl groups in the molecule is generally obtained by reacting an epoxy compound with (meth) acrylic acid and an acid anhydride. The epoxy compound used here is not particularly limited, but includes a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, or Epoxy compounds such as aliphatic epoxy compounds may be mentioned.

As the acid anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride,
Aromatic polyvalent carboxylic acid anhydrides such as pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride; 5- (2
5-dioxotetrahydrofuryl) -3-methyl-3-
Cyclohexene-1,2-dicarboxylic acid anhydride, endobicyclo- [2,2,1] -hept-5-ene-2,3
-Dicarboxylic acid anhydride etc. are mentioned.

As a urethane (meth) acrylate resin having two or more carboxyl groups in one molecule, a unit derived from a (meth) acrylate (a) having a hydroxyl group, a unit derived from a polyol (b), and a poly A compound containing a unit derived from the isocyanate (c) as a constitutional unit is preferable. In this compound, both terminals are composed of a unit derived from (meth) acrylate (a) having a hydroxyl group, and a unit derived from a polyol (b) and a polyisocyanate (c) which are linked by a urethane bond between the both terminals.
It is composed of the unit of origin. The repeating unit linked by the urethane bond has a structure in which a carboxyl group is present.

An example of a urethane (meth) acrylate compound having two or more carboxyl groups in one molecule is:
It is obtained by reacting at least a (meth) acrylate (a) having a hydroxyl group, a polyol (b) and a polyisocyanate (c), and the polyol (b) or the polyisocyanate (c).
A compound having a carboxyl group is used for at least one of the above. It is particularly preferable to use the polyol (b) having a carboxyl group.

Examples of the (meth) acrylate (a) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or oxidation of each of the (meth) acrylates. Alkylene adduct, glycerin mono (meth) acrylate,
Glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethyloldi (meth)
Examples thereof include acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and trimethylolpropane-alkylene oxide adduct-di (meth) acrylate. These (meth) acrylates (a) having a hydroxyl group can be used alone or in combination of two or more. Moreover, among these, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

As the polyol (b), a polymer polyol (b1) and / or a dihydroxyl compound (b2) can be used. Specific examples of the polymer polyol (b1) include polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, polyester polyols obtained from esters of polyhydric alcohols and polybasic acids, hexamethylene carbonate, pentamethylene. Examples thereof include polycarbonate-based diols containing units derived from carbonate and the like as constitutional units, polycaprolactone diols, polybutyrolactone diols and other polylactone-based diols.

When the polymer polyol (b1) having a carboxyl group is used, for example, a tribasic or more polybasic acid such as (anhydrous) trimellitic acid is allowed to coexist at the time of synthesizing the polymer polyol (b1). A compound synthesized so that the group remains may be used.

As the dihydroxyl compound (b2),
Branched or linear compounds with two alcoholic hydroxyl groups can be used. In particular, it is preferable to use a dihydroxy aliphatic carboxylic acid having a carboxyl group. Examples of such a dihydroxyl compound (b2) include dimethylolpropionic acid and dimethylolbutanoic acid. By using a dihydroxy aliphatic carboxylic acid having a carboxyl group, the carboxyl group can be easily present in the urethane (meth) acrylate compound.

The polymer polyol (b1) and the dihydroxyl compound (b2) may be used either individually or in combination of two or more.

Further, when a urethane (meth) acrylate compound having two or more carboxyl groups in one molecule is produced, a polymer polyol (b1) having a carboxyl group is used in combination, or a polyisocyanate (described later) ( When a compound having a carboxyl group is used as c), ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol,
1,3-butanediol, 1,5-pentanediol,
A dihydroxyl compound (b2) having no carboxyl group such as neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and hydroquinone may be used. .

Specific examples of the polyisocyanate (c) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate,
Hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m, or p) -xylene diisocyanate, methylene bis (cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate , Cyclohexane-1,4-dimethylene diisocyanate and 1,5-naphthalene diisocyanate. These polyisocyanates can be used alone or in combination of two or more. Further, a polyisocyanate (c) having a carboxyl group can be used.

The weight average molecular weight of the polycarboxylic acid resin (A) is preferably 1,000 to 100,000, more preferably 8,000 to 30,000. Here, the weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography. The weight average molecular weight of the polycarboxylic acid resin (A) is 1,000.
If the amount is less than 100%, the elongation, flexibility and strength of the cured film may be impaired, and if it exceeds 100,000, the cured film may become hard and flexibility may be deteriorated.

The acid value of the polycarboxylic acid resin (A) is 5 to 1
It is preferably 50 mgKOH / g, 30 to 12
0 mg KOH / g is more preferred. Acid value is 10mgKO
If it is less than H / g, the reactivity with the curable component may decrease and the heat resistance may be impaired. If it exceeds 150 mgKOH / g, the characteristics as a resist such as alkali resistance and electric characteristics of the cured film may deteriorate.

Throughout the present specification, the acid value of the resin is measured by the following method. About 0.2 g of the sample is precisely weighed in a 100 ml Erlenmeyer flask by a precision balance, and 10 ml of pyridine is added to this and dissolved. Further, add 1 phenolphthalein ethanol solution as an indicator to this container.
Add ~ 3 drops and stir well until sample is uniform.
This is titrated with a 0.05 N potassium hydroxide-ethanol solution, and the end point of neutralization is when the indicator is slightly reddish for 30 seconds. The value obtained by using the calculation formula below is used as the acid value of the resin. Acid value (mgKOH / g) = [B × f 5.611] / S B: amount of 0.05N potassium hydroxide-ethanol solution used (ml) f: 0.05N potassium hydroxide-ethanol solution factor S : Amount of sample (g)

Further, these polycarboxylic acid resins (A)
Can be used alone or in combination of two or more.

The curing component (B) of the present invention is one which is itself cured by heat or light such as ultraviolet rays, or the carboxyl group in the polycarboxylic acid resin (A) which is the main component in the composition of the present invention. It may also react with other functional groups (eg, hydroxyl group) by heat, ultraviolet rays, or the like.

Specific examples include epoxy resin, phenol resin, silicone resin, polyamide resin and the like. Of these, epoxy resins are preferred. Specific examples of the epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type. Epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, silicone modified epoxy An epoxy compound having two or more epoxy groups in one molecule such as a resin or an ε-caprolactone modified epoxy resin can be used. In order to impart flame retardancy, chlorine,
A halogen atom such as bromine or an atom such as phosphorus introduced into the structure in a bound state that is not easily decomposed by heat or water may be used. Further, bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylenoyl ethane resin and the like may be used.

Examples of the other curing component (B) include low molecular weight monomers and oligomers having a functional group reactive with an epoxy group or a carboxyl group or a photopolymerizable functional group. Among these curing agents (B), the photopolymerizable ones include 2
-Hydroxyethyl (meth) acrylates such as hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono, di or poly (meth) such as ethylene glycol and propylene glycol
Acrylates; N, N dimethylacrylamide, N-
Acrylamides such as methylolacrylamide; N,
Aminoalkyl (meth) acrylates such as N-dimethylaminoethyl (meth) acrylate; polyhydric alcohols such as trimethylolpropane and pentaerythritol, or mono- or poly (meth) such as ethylene oxide adducts or propylene oxide adducts thereof Acrylates; mono- or poly (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane tritriglycidyl ether, triglycidyl isocyanurate; mono- or poly (meth) acrylates of oligomers of bisphenol A; urethane compounds Mono- or poly (meth) acrylates; other polyfunctional (meth) acrylic acid ester monomers and oligomers, etc. may be mentioned.

In the thermosetting resin composition of the present invention, the curing component (B) is used alone or as a mixture of two or more kinds. The amount of the curing component (B) blended in the composition is
The amount is preferably 1 to 50% by mass, more preferably 3 to 45% by mass. When the content of the curing component (B) is less than 1% by mass, the solder heat resistance of the cured film of the thermosetting resin composition may be insufficient, and when it exceeds 50% by mass, the amount of shrinkage of the cured film may be insufficient. Flexible printed wiring board (F
When used as an insulating protective film for (PC), warpage deformation (curl) tends to increase.

The curing agent (C) of the present invention is used to further improve the properties such as adhesion, chemical resistance and heat resistance. Specific examples of such a curing agent include 2MZ, 2E4MZ, C ₁₁ Z, and C ₁₇ manufactured by Shikoku Chemicals Co., Ltd.
Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-
_{CN, C 11 Z-CN,} 2PZ-CN, 2PHZ-CN,
2MZ-CNS, 2E4MZ-CNS, 2PZ-CN
S, 2MZ-AZINE, 2E4MZ-AZINE, C
₁₁ Z-AZINE, 2MA-OK, 2P4MHZ, 2P
Imidazole derivatives such as HZ, 2P4BHZ; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide Organic acids and / or epoxy adducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S- Triazine derivatives such as triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine,
Amines such as N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyvinylphenol, polyvinylphenol bromide, phenol novolac, Polyphenols such as alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine; tri-n-
Butyl (2,5-dihydroxyphenyl) phosphonium bromide, phosphonium salts such as hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborol Ate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, manufactured by Ciba Geigy, Irgacure 261, Asahi Denka Co., Ltd., Optoma-SP-1
Cationic polymerization catalysts such as 70; styrene-maleic anhydride resins; well-known conventional substances such as equimolar reaction products of phenyl isocyanate and dimethylamine, and organic polyisocyanates such as tolylene diisocyanate and isophorone diisocyanate and equimolar reactions of dimethylamine. Examples of the curing agents or curing accelerators are

It is necessary to use an appropriate curing agent (C) depending on the type of the curing component (B) of the present invention. The curing agent (C) can be used alone or in combination of two or more. The amount of the curing agent (C) used is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of the curing component (B). When the compounding amount of the curing agent (C) is less than 0.1% by mass with respect to the curable resin composition of the present invention, curing of the composition becomes insufficient, and when it exceeds 25% by mass, the composition from the cured product becomes Sublimable components increase, which is not preferable.

Conductive filler (D) used in the present invention
Is a compound having a pH of more than 7.0 and is not particularly limited as long as it is a conductive filler used for making the resin conductive. Specific examples thereof include conductive polymers, carbon-based conductive fillers, metal powders, metal flakes, metal ribbons, metal fibers, metal oxides, non-carbon-based conductive fillers coated with a conductive substance, and the like.

As the conductive polymer, polyacetylene-based, polyphenylene-based, heterocyclic polymer, ionic polymer, ladder, network polymer and the like can be used.

Examples of the carbon-based conductive filler include carbon powder, graphite, carbon fiber, carbon flakes, and scale-like carbon. Carbon blacks such as acetylene black, oil furnace black, thermal black, and channel black are selected according to the raw material and the manufacturing method. , PAN system,
Pitch-based carbon fibers and graphites such as natural graphite and artificial graphite can be used.

The carbon type conductive filler may be surface-treated with a surface treatment agent such as titanate type, aluminum type or silane type. In addition, a quinone group present on the surface of the carbon-based conductive filler, grafted with a reactive polymer or reactive monomer that reacts with a phenolic hydroxyl group, etc., subjected to surface treatment, and using one having improved photocurability is used. Good. Further, in order to improve the workability in producing the thermosetting resin composition, a granulated product may be used.

It is also possible to use the carbon type conductive filler previously dispersed in a dispersant, a solvent or the like. As the dispersant, a surfactant, a pigment derivative, a polymer compound or the like having an affinity for the carbon-based conductive filler can be used. The solvent is not particularly limited as long as it can dissolve the polycarboxylic acid resin, but the boiling point is 120 ° C to
Organic solvents in the range of 200 ° C. are preferred. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether and the like are preferable because dispersion control is easy.

As the non-carbon type conductive filler, specific examples of metal species such as metal powder, metal flakes and metal ribbons are silver,
Nickel, copper, zinc, aluminum, stainless steel, iron,
Examples include brass, chrome and tin. Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum,
A brass etc. can be illustrated. Such metal powder, metal flakes,
The metal ribbon and the metal fiber may be surface-treated with a surface-treating agent such as titanate-based, aluminum-based or silane-based. Specific examples of the metal oxide include SnO ₂ (antimony-doped), In ₂ O ₃ (antimony-doped), ZnO.
(Aluminum dope) and the like can be exemplified, and these may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based or silane-based.

Specific examples of the conductive substance in the inorganic filler coated with the conductive substance include aluminum, nickel, silver, carbon, SnO ₂ (antimony-doped), and I.
Examples thereof include n ₂ O ₃ (antimony-doped). Further, as the inorganic filler to be coated, mica, glass beads, glass fiber, carbon fiber, potassium whisker titanate,
Examples thereof include barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide type whiskers, titanic acid type whiskers, and silicon carbide whiskers. Examples of the coating method include a vacuum vapor deposition method, a sputtering method, an electroless plating method and a baking method. Further, these may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based or silane-based.

Among the above conductive fillers (D), the inorganic compound conductive filler (D) is preferable, and more preferable is the carbon type conductive filler, and among them, carbon black is the most preferable.

The conductive filler (D) has a pH of 7.0.
It is preferably higher than pH 7.1, more preferably pH 7.1 to 10.
It is 0. When the pH is 7.0 or less, the storage stability of the thermosetting resin composition often deteriorates, which is not preferable. Further, two or more kinds of conductive fillers (D) may be used in combination.
The above pH value is a value measured by a glass electrode meter of a mixed liquid of the conductive filler (D) and distilled water, and the details of the measuring method are as described in the examples.

Further, in order to improve the dispersibility of the electrically conductive filler (D) in the composition, the electrically conductive filler (D) may be subjected to various surface treatment agents. Known fatty acid metal salts, silane-based, azidosilane-based, and titanate-based known coupling agents, and oxy-ethylenedodecyl-amine and other known surfactants can be used.

The particle size of the conductive filler (D) of the present invention varies depending on the type and shape of the conductive filler (D) used and cannot be specified unconditionally. For example, in the case of particulate carbon black, the primary particles have a particle size of 100 nm or less. Those having a thickness of 50 nm or less are more preferable.

Conductive filler (D) used in the present invention
The preferred content of is different depending on the type of the conductive filler used, so it cannot be unconditionally specified, but a cured product obtained by curing (polymerizing) the curable resin composition of the present invention, a solder resist, a protective film, etc. Surface resistance of 10 ³ to 10 ¹¹ Ω
It is desirable to set so that Usually, from the viewpoint of the balance of conductivity and fluidity, storage stability, photosensitivity, etc., 0.05 to 80% by mass, preferably 0.1% in the composition.
It is preferably in the range of -60% by mass. Particularly when the conductive filler (D) is a carbon-based conductive filler, its content is preferably in the range of 0.1 to 10 mass%.

Conductive filler (D) used in the present invention
The volume resistivity value of is preferably 1.0 × 10 ⁻¹ Ω · cm or less, more preferably 1.0 × 10 ⁻³ Ω · cm or less.

As the photopolymerization initiator (E) used in the present invention, benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, hydroxybenzophenone,
Benzophenones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl ether and other benzoin alkyl ethers, 4-phenoxydichloroacetophenone, 4-t-butyl- Dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-
1, acetophenones, thioxanthene, 2-chlorothioxanthene, 2-methylthioxanthene, thioxanthenes such as 2,4-dimethylthioxanthene, alkylanthraquinones such as ethylanthraquinone and butylanthraquinone, 2,4,6- Acylphosphine oxides such as trimethylbenzoyldiphenylphosphine oxide, benzyldimethylketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholinopropan-1-one, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Α-aminoketones such as butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
1- [4- (2-hydroxyethoxy) phenyl] -2
Examples include α-hydroxyketones such as -hydroxy-2-methyl-propan-1-one and 9,10-phenanthrenequinone. These can be used alone or as a mixture of two or more kinds.

Among these photopolymerization initiators (E),
Benzophenones, acetophenones, acylphosphine oxides, α-aminoketones and α-hydroxyketones are preferable, and particularly 4,4′-bis (diethylamino) benzophenone and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-
1,2,4,6-Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone is preferable because it has high wavelength absorption efficiency and high activity.

The blending amount of these photopolymerization initiators (E) is
A total of 100 photocurable components in the curable resin composition of the present invention.
0.1-20 mass% is preferable in mass%, 0.2-10
Mass% is more preferable. When the blending amount of the photopolymerization initiator (E) is less than 0.1% by mass, curing of the photosensitive composition may be insufficient. The photo-curing component referred to here is a polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule, a curing component (B), a diluent (F), and others added as necessary. Among these components, it means a component having a photopolymerizable functional group such as a (meth) acrylate group. Further, in the case of using a photopolymerization initiator and polymerizing and curing it with ultraviolet rays, a photosensitizer can be used in combination as necessary in order to improve the polymerization rate. As the sensitizer used for such a purpose, pyrene, perylene,
2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, phenothiazine and the like can be mentioned. When used in combination with the sensitizer, the amount used is 0.1 with respect to 100 parts by mass of the photopolymerization initiator.
The range of 100 to 100 parts by mass is preferable.

The diluent (F) is used for improving the coating property of the curable resin composition of the present invention by lowering the viscosity. Specific examples thereof include organic solvents.

Typical organic solvents include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol and butyl carbitol. , Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate and other esters, ethanol , Alcohols such as propanol, ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated stone Naphtha, petroleum solvents such as solvent naphtha, and the like. These organic solvents are removed by evaporation after coating on a printed circuit board or the like. As the diluent (F), a reactive diluent can be used in addition to the organic solvent. The reactive diluent means a low molecular weight monomer having a functional group capable of reacting with an epoxy group or a carboxyl group or a photopolymerizable functional group. The reactive diluent remains in the cured product as a curing component of the curable resin composition. It can be said that the reactive diluent has a particularly low viscosity among the curing components (B).

The diluent (F) is used alone or as a mixture of two or more kinds, and the amount of the diluent (F) used is such that the viscosity of the curable resin composition of the present invention is 500 to 500,000 mPa.
The amount set to be s is preferable, and more preferably 1,000 to 500,000 mPa · s. The proportion of the diluent in the curable resin composition of the present invention is 5
-80 mass% is preferable, and 10-70 mass% is especially preferable. The viscosity of the curable resin composition is JIS
It is a value measured according to K5400. When there is no indication of temperature, it is the value at 25 ° C.

The curable resin composition of the present invention further comprises known and commonly used inorganic fillers, organic fillers, waxes and interfaces as necessary for the purpose of improving properties such as heat resistance, hardness, thixotropy and viscosity. Activators and the like can be used.
Specific examples of the inorganic filler, barium sulfate, barium titanate, silicon oxide powder, finely powdered silicon oxide, crystalline silica, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, Known and commonly used inorganic fillers such as mica powder can be used. Specific examples of the organic filler include silicone resin, silicone rubber, and fluorine resin. Specific examples of the wax include polyamide wax and oxidized polyethylene wax. Specific examples of the surfactant include
Silicon oil, higher fatty acid ester, amide and the like can be mentioned. These fluidity modifiers may be used alone or in combination of two or more. Of these, the use of an inorganic filler is preferable because not only the fluidity of the photosensitive composition but also the heat resistance and hardness can be improved.

Further, if necessary, known conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, silica, asbestos, orben, benton,
Adhesion of well-known and commonly used thickeners such as montmorillonite, silicone-based, fluorine-based, acrylic-based, polymer-based defoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents, etc. Known and conventional additives such as a sex imparting agent can be used. Further, as other additives, for example, an ultraviolet inhibitor and a plasticizer for storage stability can be added within a range not impairing the gist of the present invention.

Further, known binder resins and polyesters (meth), such as copolymers of ethylenically unsaturated compounds such as acrylic acid esters, polyester resins synthesized from polyhydric alcohols and polybasic acid compounds, etc. )
Photopolymerizable monomers and oligomers such as acrylates, polyurethane (meth) acrylates, and epoxy (meth) acrylates can also be used as long as they do not affect the properties of the composition. These may be used as the above-mentioned reactive diluent.

Water may be added to reduce the flammability of the curable resin composition of the present invention. When water is added, the carboxyl group of the component (A) is converted to amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, By salting with a (meth) acrylate compound having a tertiary amino group such as N-dimethyl (meth) acrylamide, acryloylmorpholine, N-isopropyl (meth) acrylamide, N-methylolacrylamide, the component (A) is dissolved in water. It is preferable that it is dissolved.

In producing the resin composition of the present invention, the polycarboxylic acid resin (A) and the conductive filler (D) are used.
To prepare a resin composition (I), and then to mix the resin composition (I) with a polycarboxylic acid resin, a curable component, a curing agent, a diluent, a photoinitiator and other additives. By performing it, a curable resin composition that can obtain a stable surface resistance measurement value can be obtained. This method is more effective when the conductive filler (D) is added in an amount of 10% by mass or less,
It is particularly effective when added in an amount of 2% by mass or less. When 10% by mass or less of the conductive filler (D) is added, the polycarboxylic acid resin (A), the conductive filler (D), the curable resin (B), and the curing agent are prepared without preparing the resin composition (I). When (C), the photopolymerization initiator (E), the diluent (F) and other additives are mixed, the dispersion of the conductive filler (D) becomes poor and a resin composition having a stable surface resistance value is obtained. I can't get it. The mixing ratio of the polycarboxylic acid resin (A) and the conductive filler (D) of the resin composition (I) is 50 to 9 of the polycarboxylic acid resin (A).
0% by mass, 50 to 10% by mass of the conductive filler (D), preferably 80 to 90% by mass of the polycarboxylic acid resin (A) and 20 to 10% by mass of the conductive filler (D).

The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components by a conventional method. The mixing method is not particularly limited, and some of the components may be mixed and then the remaining components may be mixed, or all the components may be mixed at once. It is more desirable to mix the resin (A) and the conductive filler (D) first, and then mix the remaining components.

As the mixing device, for example, a resolver,
A known kneader such as a roll mill or a bead mill can be used.

The curable resin composition of the present invention is particularly useful as a resist ink, but can also be used as a paint, a coating agent, an adhesive or the like. When the composition of the present invention is used as a resist ink, examples of substrates that can be applied include polyimide films, phenol resin laminated plates, and glass epoxy resin coated plates. Since the cured product of the present invention has excellent flexibility, it is particularly suitable for a flexible substrate having a polyimide film or the like as a base material.

The resist ink composition of the present invention is cured, for example, as follows to obtain a cured product. That is, the curable resin composition of the present invention is applied to a flexible printed wiring board with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, The coating film at 100 to 200 ° C.
A method of obtaining a cured film by performing a drying / curing reaction for 1 to 2 hours can be mentioned. Further, in order to improve various physical properties, irradiation with ultraviolet rays and / or heating (for example, 100 to 200?
Sufficient curing may be performed for 0.5 to 1.0 hour).

When used as a photo-sensitive resist, the curable resin composition of the present invention containing a photo-polymerization initiator and the resist ink are applied to a substrate having a circuit formed thereon in an amount of 10 μm.
After being applied to a thickness of -100 μm, it is heat-treated in a temperature range of 60 ° C to 100 ° C for about 5 to 30 minutes and dried, and exposed through a negative mask having a desired exposure pattern to expose an unexposed portion. Remove with a developing solution and develop, 100 ℃ ~
A method of heat-treating at a temperature range of 180 ° C. for about 10 to 40 minutes and curing is exemplified. This composition is particularly suitable for use as an insulating protective film of an FPC substrate because it has excellent flexibility when it is used as a cured product, and thus it has little curl and is easy to handle. It can be a substrate. Further, it may be used as an insulating resin layer between the layers of the multilayer printed wiring board.

As the active light used for the exposure, active light generated from a known active light source such as carbon arc, mercury vapor arc, xenon arc or the like is used. Since the sensitivity of the photopolymerization initiator (E) contained in the photosensitive layer is usually maximum in the ultraviolet region, the active light source in that case is preferably one which effectively emits ultraviolet light. Of course, those in which the photopolymerization initiator (E) is sensitive to visible light, for example,
In the case of 9,10-phenanthrenequinone or the like, visible light is used as the active light, and a photographic flood light bulb, a sun lamp, or the like is used as the light source in addition to the active light source. As the developing solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used.

Curing (polymerization) of the curable resin composition of the present invention
The surface resistance of the cured product, solder resist, protective film, etc. obtained by the above is preferably 10 ³ to 10 ¹¹ Ω,
More preferably 10 ³ to 10 ¹⁰ Ω, and 10 ⁴ to 1
More preferably, it is 0 ¹⁰ Ω. Surface resistance is 10 ³ Ω
If it is less than 10 ¹¹ Ω, there is a risk of electrical continuity between the circuits of the printed wiring board. On the other hand, if it exceeds 10 ¹¹ Ω, the antistatic performance becomes insufficient.

[0068]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Production Example 1 An average value of Production Example n of an epoxy acrylate resin (hereinafter referred to as “EAR”) containing a diluent (F) is 3.3, an epoxy equivalent is 650, and a softening point is:
81.1 ° C, melt viscosity (150 ° C): 12.5 mPa
371 g of the bisphenol A type epoxy resin represented by the formula (1), which is s, is dissolved in 925 g of epichlorohydrin and 462.5 g of dimethyl sulfoxide, and then 52.8 g of 98.5% NaOH is added over 100 minutes at 70 ° C. under stirring. Added. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Then, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 g of methyl isobutyl ketone, and further 30% by mass N 2
10 g of an aOH aqueous solution was added and the reaction was carried out at 70 ° C. for 1 hour.
After the reaction was completed, the product was washed twice with 200 g of water. After separation of oil and water, methyl isobutyl ketone was distilled and recovered from the oil layer,
Epoxy equivalent 287, hydrolyzable chlorine content 0.07
%, Softening point 64.2 ° C., melt viscosity 7.1 mPa · s (1
340 g of epoxy resin (a-1) having a temperature of 50 ° C. was obtained. 2870 g (10 equivalents) of the obtained epoxy resin (a-1), 720 g (10 equivalents) of acrylic acid, 2.8 g of methylhydroquinone, carbitol acetate 1943.
5 g was charged, the mixture was heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, the reaction solution was cooled to 60 ° C., 16.6 g of triphenylphosphine was charged, the mixture was heated to 100 ° C. and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, add 783 g of succinic anhydride to this.
(7.83 mol), carbitol acetate 421.6
g, heated to 95 ° C., reacted for about 6 hours, cooled, an epoxy having a solid content acid value of 100 mgKOH / g, and a solid content concentration of 65% diluted with carbitol acetate. An acrylate resin EPA was obtained.
The viscosity of the obtained EAR was 250 mPa · s (25 ° C).

[Chemical 1]

Production Example 2 Production of Urethane Acrylate Compound "PUA-1" Containing Diluent (F) In a reaction vessel equipped with a stirrer, thermometer, condenser,
Polycaprolactone diol as a polymer polyol (PLACCEL21 manufactured by Daicel Chemical Industries Ltd.)
2, molecular weight 1250), 3750 g (= 3 mol), dimethylolpropionic acid as a dihydroxyl compound having a carboxyl group, 402 g (= 3 mol), isophorone diisocyanate as a polyisocyanate 15
54 g (= 7 mol) and 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, 238 g (= 2.05 mol), and further p-
1.0 g each of methoxyphenol and di-t-butyl-hydroxytoluene were added. The mixture was heated to 60 ° C. with stirring and stopped, and 1.6 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel begins to drop, it is heated again and stirring is continued at 80 ° C., and the absorption spectrum of the isocyanate group (2280
(cm ^-1 ) was confirmed to have disappeared, and the reaction was terminated. Carbitol acetate was added so that the solid content was 50% by mass to obtain a viscous liquid urethane acrylate compound PUA-1 containing the diluent (F). The weight average molecular weight of the obtained urethane acrylate (excluding carbitol acetate) was 25,000 (the average molecular weight was determined by gel carrier liquid chromatography (GPC Showa Denko GPC-
The value was converted to polystyrene using 1). ),
The acid value of the solid content was 40 mgKOH / g.

Production Example 3 Production of "PUA-2" of Urethane Acrylate Compound Containing Diluent (F) Polytetramethylene glycol (PTG-850SN, Hodogaya Chemical Co., Ltd., molecular weight 8) as polymer polyol
50) 850 g (= 1 mol), dimethylolpropionic acid 938 g (= 7 mol) as a dihydroxyl compound having a carboxyl group, and isophorone diisocyanate 1998 g (= 9 mol) as a polyisocyanate.
Was thrown in. Heat to 60 ° C with stirring and stop,
1.4 g of dibutyltin dilaurate was added. When the temperature inside the reaction vessel begins to drop, reheat to 80 ° C and
Stirring was continued while maintaining the temperature at 5 to 85 ° C., and when the residual NCO concentration reached the theoretical value, the reaction was stopped to synthesize a urethane oligomer. Furthermore, 0.9 g each of p-methoxyphenol and di-t-butyl-hydroxytoluene
After introducing each into the reaction vessel, 238 g (= 2.05 mol) of 2-hydroxyethyl acrylate as an acrylate having a hydroxyl group was added to restart the reaction. The reaction was terminated by confirming that the absorption spectrum of the isocyanate group (2280 cm ^-1 ) had disappeared in the infrared absorption spectrum. Carbitol acetate was added so that the solid content was 45% by mass to obtain a viscous liquid urethane acrylate compound PUA-2. The obtained urethane acrylate (excluding carbitol acetate) had a weight average molecular weight of 16,000 and an acid value of 90 mgKOH / g.

<Production of Curable Resin Composition> Commercial products used in the following Examples and Comparative Examples are as follows.

Curing component (B) ZNA-115: bifunctional (meaning the number of acrylic acid residues) acrylic acid ester oligomer KAYARAD
ZNA-115 (manufactured by Nippon Kayaku Co., Ltd.) (number of acrylic acid residues) YL-6121H: a mixture of tetramethylbiphenol type epoxy resin and biphenol type epoxy resin (manufactured by Yuka Shell Co.) Urethane acrylate-1: 6 functional urethane Acrylate monomer EB1290K (manufactured by Daicel Chemical Industries Ltd.) Acrylate-2: 2 functional urethane acrylate oligomer UF8001 (manufactured by Kyoeisha Chemical Co., Ltd.) DCPA-120: 6 functional acrylic ester monomer KAYARAD DCPA-120 (manufactured by Nippon Kayaku Co., Ltd.)

Curing agent (C) PC-1: Melamine (manufactured by Nissan Chemical Industries, Ltd.)

Conductive filler (D) M880: MONARCH 880 (pH value 8.
5) BP2000: BLACK PEARLS 2000
(PH value 8.6) BP130: BLACK PEARLS 130 (p
H value 8.0) M1000: MONARCH 1000 (pH value 2.
5) Made by Cabot Specialty Chemicals Inc.

Photopolymerization Initiator (E) TPO: 2,4,6-trimethylbenzoylphenylphosphine oxide TPO (manufactured by BASF) IRGACURE 369: (manufactured by Ciba Specialty Chemicals) EAB-F: 4,4 '-Bis (diethylamino) benzophenone EAB-F (Hodogaya Chemical Co., Ltd.) DETX-S: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.)

Diluent (F) Carbitol Acetate: Daicel Chemical Co. # 8500: Mixture of carbitol acetate and petroleum naphtha, Japan Polytec

Filler Barium sulfate: made by Sakai Chemical Industry Silica: AEROSIL, manufactured by Nippon Aerosil Co., Ltd.

Examples 1 to 5 and Comparative Examples 1 to 2 Polycarboxylic acid resin (A) 9 containing the diluent (F) shown in Table 1
0% by mass and 10% by mass of the conductive filler (D) were mixed (23 ° C.) with a 4-inch triple roll (manufactured by Inoue Seisakusho),
The obtained resin composition and polycarboxylic acid resin (A), curing component (B), curing agent (C), conductive filler (D) and diluent (F), and commercially available fillers (barium sulfate, silica) And are mixed by a 4-inch three-roll mill so that the blending ratio (mass%) shown in Table 1 is finally obtained (23 ° C)
Then, a curable resin composition was prepared. As the polycarboxylic acid resin component, the resin "EAR" produced in Production Example 1 above was used. The EAR contains carbitol acetate as a diluent (F).

[Examples 6 to 9 and Comparative Examples 3 to 4] Polycarboxylic acid resin (A) 9 containing the diluent (F) shown in Table 2
0% by mass and 10% by mass of the conductive filler (D) were mixed by a 4-inch triple roll (23 ° C.), and the obtained resin composition, polycarboxylic acid resin (A), curing component (B), curing agent (C), conductive filler (D), photopolymerization initiator (E)
A diluent (F) and a commercially available filler were mixed (at 23 ° C.) with a 4-inch triple roll so that the final blending ratio (mass%) shown in Table 2 was obtained to prepare a curable resin composition. . As the polycarboxylic acid resin component, the resins "PUA-1", "PUA-2", and "EA" produced in the above production examples
R ”was used. These contain carbitol acetate as a diluent (F).

[Preparation 1 of Cured Product] The curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 had a film thickness of 2 after curing.
It is applied on a substrate for evaluation (copper foil-bonded glass fiber reinforced epoxy resin substrate having a copper thickness of 35 μm) by a screen printing method so as to be 0 to 40 μ, and the coating film is heat cured for 30 minutes by a hot air dryer at 150 ° C. It was With respect to the test piece having the obtained cured film, the physical properties of storage stability and surface resistance described below were evaluated.

[Cured Product Preparation 2] Examples 6 to 9 The curable resin compositions obtained in Comparative Examples 3 and 4 had a film thickness of 2 after curing.
It is coated on a substrate for evaluation (copper foil-bonded glass fiber reinforced epoxy resin substrate having a copper thickness of 35 μm) by a screen printing method so as to have a thickness of 0 to 40 μm, and is dried with a hot air dryer at 70 ° C.
It was dried for a minute. After allowing the coating film to cool to room temperature, exposing it with a metal halide lamp (1 J / cm ² , wavelength 365 nm conversion, scattered light), and using a 1 mass% sodium carbonate aqueous solution at room temperature 30 ° C. and a spray pressure of 0.2 MPa, 1 Developed for minutes. Further, it was heat-treated at 150 ° C. for 30 minutes using a hot air dryer to obtain a cured product. The obtained test piece was evaluated for each physical property such as storage stability, developability, photosensitivity, and surface resistance described below.

(PH Value of Conductive Filler) 5 g of the conductive filler was weighed in a hard Erlenmeyer flask for pH measurement, 100 ml of purified water was added, and the mixture was boiled for 5 minutes. At this time, the evaporated weight loss was supplemented with boiled purified water, sealed, and cooled to 23 ° C. This supernatant was transferred to a beaker and measured by a pH measuring method (23 ° C.) using a glass electrode described in JIS Z8802-7.

(Storage stability) The resin composition stored in a closed container was placed in a constant temperature bath at 40 ° C., and the number of days when gel was generated in the resin composition was visually measured.

(Surface resistance) A commercially available comb pattern substrate (IPC standard ANCI / ICP-SM-840B, ICP-B25) is used as a substrate for evaluation.
Test pieces were prepared in accordance with Preparations 1 and 2 of the cured product except that the test base / type B) was used. 23 for each test piece
After conditioning for 24 hours in an atmosphere of 50 ° C and 50% RH,
The surface resistance value was measured with a resistance measuring device PRS-801 manufactured by ROSTAT.

(Photosensitivity) The film thickness after curing the curable resin compositions obtained in Examples 6 to 9 and Comparative Examples 3 and 4 was 20 to 25.
It was applied to a substrate for evaluation (copper foil-coated glass fiber reinforced epoxy resin substrate having a copper thickness of 35 μm) by a screen printing method so as to have a thickness of μm, and dried by a hot air dryer at 80 ° C. for 30 minutes. After allowing the coating film to cool to room temperature, use a step tablet (21 step tablet manufactured by Hitachi Chemical Co., Ltd.) to expose with a metal halide lamp (1 J / c).
m ² , wavelength 365 nm conversion, scattered light). After that, development and heat treatment were performed in the same manner as in Production 2 of cured product, and the number of stages of the cured product remaining on the substrate was measured to evaluate the photosensitivity of the photosensitive composition. The light sensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of this step tablet, the higher the light sensitivity.

(Developability) The curable resin compositions obtained in Examples 6 to 9 and Comparative Examples 3 and 4 had a film thickness of 20 to 25 after curing.
It is applied to the evaluation substrate (copper thickness 35 μm) by the screen printing method so as to have a thickness of
It was dried for 0 minutes. It was used as a 1 mass% sodium carbonate aqueous solution and developed at room temperature of 30 ° C. and a spray pressure of 0.2 MPa for 1 minute. The developing property was judged by visually observing the degree of residue of the resin composition or the like on the substrate in the following three stages. ◯: No development residue Δ: Some development residue X: Development residue The above evaluation results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

[0088]

EFFECT OF THE INVENTION The curable resin composition of the present invention is a one-part composition excellent in storage stability using a specific conductive filler (D). Further, the cured product not only exhibits excellent antistatic property, but also has resistance to plating, chemical resistance, high heat resistance,
It has excellent characteristics such as photosensitivity, developability, and flexibility. Therefore, the printed wiring board, which is partially or entirely coated with this cured product, is suitable for use in electronic devices that require measures against static electricity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/004 501 G03F 7/004 501 7/027 512 512 7/027 512 515 515 H05K 3/28 H05K 3 / 28 DF Term (Reference) 2H025 AA06 AA10 AA19 AB15 AB20 AC01 AD01 BC13 BC66 BC74 BC81 BJ00 CA00 CB30 CC09 CC17 4J002 BC07Y CC03X CC04Y CD02X CD05X CD06X CD12X CD13X CD20W CD20X CK02W CL00X DA76 EN006 ET017 EU047 EU077 EU117 EU187 EW017 EW047 EW177 FA018 FA048 FD118 FD14Y FD147 GQ05 4J031 AA19 AA41 AA47 AA55 AA59 AB01 AC03 AD01 AE07 AF23 AF26 5E314 AA25 AA27 AA32 AA43 BB02 BB01 BB02 BB06 BB06 BB06 BB06 BB06

Claims (16)

[Claims] 1. A polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule, a curing component (B), a curing agent (C) and a conductive filler (D) having a pH of more than 7.0. A curable resin composition comprising: 2. An epoxy (meth) acrylate resin or urethane (meth) acrylate in which a polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule has two or more carboxyl groups in one molecule. The curable resin composition according to claim 1, which is a resin. 3. The curable resin composition according to claim 2, which contains a photopolymerization initiator (E). 4. The curable resin composition according to claim 1, further comprising a diluent (F). 5. The acid value of the polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule is 5 to 150 mg.
KOH / g and weight average molecular weight of 1,000 to 10
It is 10,000, The curable resin composition as described in any one of Claims 1-4. 6. The curable resin composition according to claim 1, wherein the curing component (B) is an epoxy resin having two or more epoxy groups in one molecule. . 7. The curable resin composition according to claim 1, wherein the conductive filler (D) is carbon black. 8. A viscosity of 500 to 500,000 mPa · s.
The curable resin composition according to any one of claims 1 to 7, wherein 9. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 8. 10. The cured product according to claim 9, which has a surface resistance of 10 ³ to 10 ¹¹ Ω. 11. A resist ink containing the curable resin composition according to claim 1. 12. A solder resist comprising the cured product according to claim 9 or 10. 13. A protective film comprising the cured product according to claim 9. 14. A printed wiring board partially or entirely coated with the cured product according to claim 9. 15. A step (I) and a step (I) of mixing a polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule and a conductive filler (D) having a pH of more than 7.0. The resulting mixture has a polycarboxylic acid resin (A) having two or more carboxyl groups in one molecule, a curing component (B), a curing agent (C), and optionally a photopolymerization initiator (E), A method for producing a curable resin composition, which comprises the step (II) of mixing a diluent (F). 16. A method of preventing electrification of a resist ink, which comprises adding a conductive filler (D) having a pH of more than 7.0.