TW201942668A - Photosensitive resin composition, two-fluid photosensitive resin composition, dry film, and printed wiring board having properties of high heat resistance, and prevention of reduced adhesion strength - Google Patents

Abstract

The present invention provides a photosensitive resin composition with high heat resistance, prevention property of reduced adhesion strength, and thermal cycling resistance. The photosensitive resin composition of the present invention is characterized in containing: at least one of a carboxyl group-containing resin, talc, and mica; a bifunctional or higher functional (meth) acrylate with an isocyanuric acid ring; an epoxy resin; and a photopolymerization initiator.

Description

Photosensitive resin composition, two-liquid type photosensitive resin composition, dry film, and printed wiring board

The present invention relates to a photosensitive resin composition, a two-liquid photosensitive resin composition, a dry film, and a printed wiring board.

Generally, for printed wiring boards used in electronic equipment, etc., when mounting electronic components on the printed wiring board, it is necessary to prevent the solder from adhering to unnecessary parts, and to form a resistance in the area where the connection holes on the substrate where the circuit pattern is formed are removed. Solder layer. Nowadays, a solder resist layer is a hardened product in which a photosensitive resin composition is coated on a substrate, and a pattern is formed after exposure and development. The pattern-forming resin is hardened by heating or light irradiation. Forming a solder resist has become mainstream, and generally, such a photosensitive resin composition is required to have high solder heat resistance.

In recent years, the development of electric automobiles is progressing rapidly, and the above-mentioned substrate for forming a solder resist layer is applied.
The power semiconductors for controlling large electric power such as electric cars, hybrid cars, and wind power generators have a large amount of heat, and the substrate suitable for this is used in a high temperature environment for a long time. Therefore, it is expected that the photosensitive resin composition not only has heat resistance, but also does not reduce adhesion under such a high-temperature environment, but has high adhesion reduction resistance.
In addition, the power semiconductor is extremely high temperature when it is energized, and becomes low temperature when it is not energized. Repeatedly, cracks are easily generated in the solder resist layer, and the photosensitive resin composition is required to have high cold and heat cycle resistance.

Among them, in Patent Document 1, a photosensitive resin composition containing a photosensitive insulating resin, a thermosetting insulating resin, a polyfunctional acrylate having a triazine ring, and acrylonitrile butadiene is proposed, but its adhesion is prevented from decreasing. There is still room for improvement in heat resistance and cold and heat cycle resistance.

In Patent Document 2, the triglycidyl triisocyanurate of the photosensitive resin composition is added for the purpose of improving heat resistance. However, in recent years, this use has been gradually controlled due to the impact on the environment such as the modification caused by mutation.
Moreover, the hardened | cured material formed using this photosensitive resin composition has a problem that the cold-heat cycle resistance deteriorates. Therefore, a photosensitive composition having excellent heat resistance and cold-heat cycle resistance is expected.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] JP 2003-66603
[Patent Document 2] Japanese Unexamined Patent Publication No. 9-185167

[Problems Solved by the Invention]

Therefore, an object of the present invention is to provide a photosensitive resin composition having high heat resistance, prevention of adhesion reduction, and resistance to cold and heat cycles. Another object of the present invention is to provide a dry film, a cured product, and a printed wiring board formed using the photosensitive resin composition.

[Means for solving problems]

The photosensitive resin composition of the present invention is characterized by containing at least one of a carboxyl group-containing resin, talc and mica, a bifunctional or higher (meth) acrylate having an isotricyanic acid ring, and an epoxy resin. With photopolymerization initiator.

In the aspect of the present invention, as the carboxyl group-containing resin in the photosensitive resin composition, at least any one of a novolak type carboxyl group-containing resin and a bisphenol type carboxyl group-containing resin is preferable.

In the aspect of the present invention, the photosensitive resin composition preferably contains at least one of silicon oxide and aluminum oxide.

In the aspect of the present invention, it is preferable that the photosensitive resin composition contains a bifunctional or more (meth) acrylate having no isocyanuric acid ring.

In the aspect of the present invention, it is preferable that the photosensitive resin composition contains fluorine-containing mica as mica.

The two-liquid curable photosensitive resin composition of the present invention is composed of a first composition and a second composition, and is characterized in that:
The first composition contains a carboxyl group-containing resin and a photopolymerization initiator;
The second composition contains an epoxy resin;
At least one of the first composition and the second composition contains at least one of talc and mica; and at least one of the first composition and the second composition contains a bifunctional having an isocyanuric ring The above (meth) acrylate.

In the aspect of the present invention, the first composition preferably contains at least one of talc and mica.

In the aspect of the present invention, it is preferable that the second composition contains a bifunctional or higher (meth) acrylate having an isocyanuric acid ring.

In the aspect of the present invention, the first composition preferably contains at least one of silicon oxide and aluminum oxide.

In the aspect of the present invention, it is preferable that the first composition contains a bifunctional or more (meth) acrylate having no isocyanuric ring.

The dry film of the present invention is characterized by comprising: a film; and a resin layer obtained by applying the photosensitive resin composition or the two-liquid type photosensitive resin composition to a film and drying the film.

The printed wiring board of the present invention is obtained by curing the photosensitive resin composition, the two-liquid type photosensitive resin composition, or the resin layer of the dry film.

[Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition having high heat resistance, prevention of reduction in adhesion, and resistance to cold and heat cycles. Moreover, according to another aspect of this invention, the dry film, hardened | cured material, and printed wiring board formed using the said photosensitive resin composition can be provided.

[Form of Implementing Invention]

[Photosensitive resin composition in the first aspect]
In the first aspect, the photosensitive resin composition includes at least one of a carboxyl group-containing resin, talc, and mica, and a bifunctional or higher (meth) acrylate having an isotricyanate ring, and an epoxy resin. With photopolymerization initiator.
The photosensitive resin composition may contain inorganic fillers other than talc and mica (hereinafter referred to as other inorganic fillers), a bifunctional or more (meth) acrylate having no isocyanuric ring, a colorant, and At least one organic solvent.
Each component will be described in detail below.

[(1) Carboxyl-containing resin]
As the carboxyl group-containing resin, it can be used for various conventionally known resins having a carboxyl group in the molecule. The photosensitive resin composition is a resin having a carboxyl group, and can impart alkali developability to the photosensitive resin composition.
In particular, a carboxyl group-containing resin having an ethylenically unsaturated double bond in a molecule is preferred from the viewpoint of photohardenability or development resistance. The ethylenically unsaturated double bond is preferably acrylic acid or methacrylic acid or one derived from these derivatives.
When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, it can be obtained by using a (meth) acrylate such as a bifunctional or more (meth) acrylate having an isotricyanate ring as described later in combination. The composition is photosensitive.
Specific examples of the carboxyl group-containing resin include the following compounds (either an oligomer or a polymer may be used).

(1) Copolymerization of unsaturated carboxylic acids such as (meth) acrylic acid with compounds containing unsaturated groups such as styrene, α-methylstyrene, lower alkyl (meth) acrylates, and isobutylene Carboxyl-containing resin.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl-containing diisocyanates such as dimethylolpropionic acid and dimethylolbutanoic acid Alcohol compounds and having polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-epoxide adduct glycols, and phenolic hydroxyl groups Carboxyl group-containing urethane resin for polyaddition reaction of glycol compounds such as alcoholic hydroxyl compounds and the like.

(3) with diisocyanate, with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin (Meth) acrylates of bifunctional epoxy resins such as bisphenol-type epoxy resins, or partially acid anhydride modified products thereof, carboxyl group-containing diol compounds, and polyaddition reactions of diol compounds, carboxyl group-containing photosensitive amines Urethane resin.

(4) In the synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth) acrylfluorenyl groups added to a molecule such as a hydroxyalkyl (meth) acrylate, On the other hand, a carboxyl group-containing photosensitive urethane resin is subjected to terminal (meth) acrylation.

(5) In the synthesis of the resin of (2) or (3) above, add a mole reactant such as isophorone diisocyanate and pentaerythritol triacrylate, etc., and have 1 isocyanate group and 1 or more in the molecule. (Meth) acrylfluorene-based compound, and a terminal (meth) acrylated carboxyl group-containing photosensitive urethane resin.

(6) A carboxyl group-containing photosensitive resin which reacts (meth) acrylic acid with a bifunctional or higher polyfunctional (solid) epoxy resin, and adds a dibasic acid anhydride to a hydroxyl group present in a side chain.

(7) A polyfunctional epoxy resin that further epoxidizes the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and (meth) acrylic acid to react a dibasic acid anhydride with the generated hydroxyl group Addition of carboxyl-containing photosensitive resin.

(8) A bifunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and phthalic anhydride and Carboxyl-containing polyester resin with addition of dibasic acid anhydrides such as hydrogen phthalic anhydride and hexahydrophthalic anhydride.

(9) For an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (A Group) unsaturated monocarboxylic acids, such as acrylic acid, are reacted. For the alcoholic hydroxyl groups of the obtained reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups with epoxides such as ethylene oxide and propylene oxide in one molecule, and reacting a monocarboxylic acid containing an unsaturated group with respect to the obtained product A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(11) A reaction organism obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate, propylene carbonate, etc. Carboxylic photosensitive resin obtained by reacting carboxylic acid and reacting the obtained reaction product with polybasic acid anhydride.

(12) For the resins of the above (1) to (11), a carboxyl group-containing compound obtained by adding a compound having one epoxy group and one or more (meth) acrylfluorenyl groups in one molecule is further added. Photosensitive resin.
In addition, in this specification, (meth) acrylate is a term which uses acrylate, methacrylate, and these mixtures as a generic term, and it is the same also about other similar expressions.

The acid value of the carboxyl group-containing resin is preferably 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is set to 40 mgKOH / g or more, alkaline development can be made favorable. Moreover, when the acid value is set to 150 mgKOH / g or less, it is easy to draw a good resist pattern. It is preferably 50 to 130 mgKOH / g.

Although the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferred to be 2,000 to 150,000. When the weight average molecular weight is set to 2,000 or more, non-stick performance or resolution can be improved. When the weight average molecular weight is set to 150,000 or less, developability and storage stability can be improved. It is preferably 5,000 to 100,000.

The compounding amount of the carboxyl group-containing resin in the photosensitive resin composition is preferably 20 to 60% by mass in terms of solid content. When it is 20% by mass or more, the coating film strength can be further increased. When it is set to 60% by mass or less, the viscosity can be made appropriate and the printability can be improved. It is preferably 30 to 50% by mass.

[(2) Talc and Mica]
The photosensitive resin composition contains at least one of talc and mica, and thereby, it is possible to improve the adhesion reduction prevention property and the cold-heat cycle resistance of the photosensitive resin composition.

The average particle diameter (D50) of talc is preferably from 0.1 μm to 100 μm, and more preferably from 1 μm to 50 μm. By setting the particle diameter within the range, the dispersibility of talc in the photosensitive resin composition can be further improved.
Among them, D50 means a particle size in which 50% of the volume is obtained by using a laser diffraction scattering particle size distribution measurement method based on Mie scattering theory. More specifically, the particle size distribution of the fine particles is prepared on a volume basis by a laser diffraction scattering particle size distribution measurement device, and the median diameter can be measured as the average particle diameter. As the measurement sample, it is preferable to use fine particles dispersed in water by ultrasonic waves. As a laser diffraction type particle size distribution measuring device, LA-500 manufactured by Horiba, Ltd. can be used.

When the compounding amount of the talc in the photosensitive resin composition is converted into solid content, it is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass for 100 parts by mass of the carboxyl group-containing resin. This makes it possible to further improve the adhesion reduction resistance of the photosensitive resin composition and the resistance to cold and heat cycles.

The mica used in the present invention may be swellable, non-swellable, synthetic, or non-synthetic. Among the various types of mica, fluorine-containing mica is used. good. By using fluorine-containing mica, the heat resistance and cold-heat cycle resistance of the photosensitive resin composition can be further improved.

The average particle diameter (D50) of mica is preferably from 0.1 μm to 500 μm, and more preferably from 1 μm to 300 μm. When the particle diameter is within this range, the dispersibility of mica in the photosensitive resin composition can be further improved.

When the compounding amount of mica in the photosensitive resin composition is converted to solid content, for 100 parts by mass of the carboxyl group-containing resin, it is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass. . Thereby, the heat resistance of the photosensitive resin composition, the prevention of adhesion reduction, and the cold-heat cycle resistance can be further improved.

[(3) Bifunctional or higher (meth) acrylate having an isocyanuric ring]
The photosensitive resin composition contains a (meth) acrylic acid ester having a bifunctional or higher function of an isocyanuric acid ring, thereby improving the heat resistance of the photosensitive resin composition, preventing the decrease in adhesion, and the resistance to cold and heat cycles.

Examples of the bifunctional or more (meth) acrylate having an isotricyanate ring include ethoxylated isocyanurate di (meth) acrylate and ethoxylated isocyanurate. Acid tri (meth) acrylate, propoxylated isocyanurate di (meth) acrylate, propoxylated isocyanurate tri (meth) acrylate, and these caprolactone modified products.

The amount of the (meth) acrylic acid ester having a bifunctional or higher isocyanuric acid ring in the photosensitive resin composition is 1 to 100 parts by mass of the carboxyl group-containing resin when converted to solid content. It is preferably 50 parts by mass, and more preferably 5 to 40 parts by mass. Thereby, the heat resistance of the photosensitive resin composition, the prevention of adhesion reduction, and the cold-heat cycle resistance can be further improved.

[(4) Epoxy resin]
Examples of usable epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, and bisphenol S. Epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentyl Diene epoxy resin, triphenylmethane epoxy resin, etc.
These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the sold epoxy resin include jER828, 806, 807, YX-8000, 8034, jER834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170 manufactured by Nippon Steel & Sumikin Corporation, ZX-1059, ST-3000, 830, 835, 840, 850, N-730A, N695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Co., Ltd.

When the epoxy group equivalent of the epoxy resin in the photosensitive resin composition is converted into solid content, the equivalent of the carboxyl group of the carboxyl group-containing resin is preferably 0.3 to 3.0. When it is 0.3 equivalents or more, the residue of a carboxyl group in a cured film can be prevented, and good heat resistance, alkali resistance, and electrical insulation properties can be obtained. On the other hand, when the blending amount is set to 3.0 equivalents or less, the low-molecular-weight cyclic (thio) ether can be prevented from remaining on the dried coating film, and the strength of the cured film can be ensured well.

[(5) Photopolymerization initiator]
Examples of usable photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-acetone and 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and other α-aminoacetophenone-based photopolymerization initiators: 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1 -Fluorene 4- [4- (2-hydroxy-2-methyl-propanyl) -benzyl] phenylfluorene-2-methyl-propane-1-one, 2-hydroxy-2-methyl- Hydroxyacetophenone-based photopolymerization initiators such as 1-phenylpropane-1-one; bis- (2,6-dichlorobenzyl) phenylphosphine oxide, bis- (2,6-dichlorobenzene (Methylfluorenyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzylfluorenyl) -4-propylphenylphosphine oxide, bis- (2,6-dichloro Benzamidine) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzyl)- 2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,5-dimethylphenylphosphine oxide Bis- (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,6-dimethoxybenzylidene diphenylphosphine oxide, 2,6-dichlorobenzidine Diphenylphosphine oxide, 2,4,6-trimethylbenzylphenylphosphonic acid methyl ester, 2-methylbenzyldiphenylphosphine oxide, neopentylphenylphenylphosphonic acid Isopropyl ester, 2,4,6-trimethylbenzylidene diphenyl phosphine oxide and other fluorenyl phosphine oxide-based photopolymerization initiators; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether , Benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether and other benzoin-based photopolymerization initiators; benzoin alkyl ether-based photopolymerization initiators; benzophenone, p-methyldi Photopolymerization of benzophenones, such as benzophenone, mignonone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone Starter; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone Acetophenone-based photopolymerization initiators such as ketones, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-acetone ; Thioxanthone, 2-ethylthio Xanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2, Thioxanthone-based photopolymerization initiators such as 4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthracene Anthraquinone-based photopolymerization initiators such as quinone, 1-chloroanthraquinone, 2-pentylanthraquinone, and 2-aminoanthraquinone; acetone dimethyl ketal, benzyl dimethyl ketal, etc. Ketone photopolymerization initiator; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p-dimethylbenzoate ethyl ester, etc. Benzoate-based photopolymerization initiators; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzidine oxime)], ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetimoxime) and other oxime ester-based photopolymerization initiators; bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl)- Titanocene-based photopolymerization initiators such as bis [2,6-difluoro-3- (2- (1-pyrrole-1-yl) ethyl) phenyl] titanium and the like.
The photopolymerization initiator may be used singly or in combination of two or more kinds.

The commercially available α-aminoacetophenone-based photopolymerization initiators include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins.
Examples of commercially available fluorenylphosphine oxide-based photopolymerization initiators include Omnirad TPO, Omnirad 819, and the like manufactured by IGM Resins.

Moreover, it can also apply to the photoinitiator which has two oxime ester group in a molecule | numerator, Specifically, the oxime ester compound which has a carbazole structure shown by the following general formula is mentioned.

In the above formula, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (from an alkyl group having 1 to 17 carbon atoms and 1 to 8 carbon atoms) Alkoxy, amine, alkylamino or dialkylamino with 1 to 8 carbon atoms), naphthyl (by alkyl with 1 to 17 carbon atoms, 1 to 8 carbon atoms) Alkoxy, amine, alkylamino or dialkylamino of 1 to 8 carbons), and Y and Z each represent a hydrogen atom, an alkyl of 1 to 17 carbons, and a carbon number 1 to 8 alkoxy, halo, phenyl, phenyl (from alkyl having 1 to 17 carbons, alkoxy having 1 to 8 carbons, amine, 1 to 8 alkyls Alkylamino or dialkylamino substituted), naphthyl (by alkyl having 1 to 17 carbons, alkoxy having 1 to 8 carbons, amino, alkyl having 1 to 8 carbons Alkylamino or dialkylamino)), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylidene, vinylidene, Diphenylene, pyridyl, naphthyl, thiophene, anthracene, thienylene, furfuryl, 2,5-pyrrole-diyl, 4,4'- - diyl, 4,2' styrene - two group, n is an integer of 0 or 1.

In the above formula, X and Y are each methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthyl, thiophene, or thiophene.

In addition to the photopolymerization initiator described above, a benzoin compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound may be used as the photopolymerization initiator. Agent.
However, rather than using these alone as a photopolymerization initiator, the above-mentioned photopolymerization initiator can be used in combination as a photopolymerization initiator or sensitizer, and it is preferable for the user.
Among the above, from the viewpoint of deep hardening, a thioxanthone compound and a tertiary amine compound are preferable, and a thioxanthone compound is more preferable.
Moreover, you may use 2 or more types of these compounds together.

When the amount of the photopolymerization initiator in the photosensitive resin composition is converted to solid content, it is preferably 1 to 50 parts by mass, and 1 to 20 parts by mass for 100 parts by mass of the carboxyl group-containing resin. Which is better. Thereby, the hardenability of a deep part can be improved.
When the photosensitive resin composition contains the above-mentioned benzoin compound as a photopolymerization starting aid, etc., when the compounding amount is converted to solid content, it is 0.01 to 10 parts by mass for 100 parts by mass of the carboxyl group-containing resin. It is preferably, and 0.1 to 5 parts by mass is more preferable.
Thereby, the hardenability of a deep part can be improved.

[(6) Other inorganic fillers]
The photosensitive resin composition of the present invention is preferably one containing an inorganic filler other than talc and mica. This makes it possible to further increase the adhesion reduction resistance of the photosensitive resin composition and the resistance to cold and heat cycles.

Examples of other inorganic fillers include silicon oxides such as amorphous silica, crystalline silica, fused silica, and spherical silica, alumina, calcium oxide, magnesium oxide, zinc oxide, and calcium carbonate. , Magnesium carbonate, fly ash, dewatered sludge, natural silicon dioxide, synthetic silicon dioxide, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, silicon Calcium acid, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, xonotlite, boron nitride, aluminum borate, silica ball, glass flake, glass ball, Silicon dioxide, iron slag, copper, iron, iron oxide, ferrosilicon, aluminum nickel cobalt magnet, various ferrite and other magnetic powder, cement, glass powder, Neuburg silica, diatomite, trioxide Antimony, magnesium oxysulfuric acid, water and aluminum, water and gypsum, alum and barium sulfate. Other inorganic fillers may be used alone or in combination of two or more.
Among the above, it is also preferable to contain at least one of silicon oxide and aluminum oxide, and the two types of spherical silicon dioxide and aluminum oxide can be used in combination, since the heat resistance of the photosensitive resin composition can be significantly improved and The resistance to cold and heat cycles is better.

The average particle diameter (D50) of other inorganic fillers is preferably from 0.1 to 100 μm, and more preferably from 0.1 to 50 μm.

When the amount of other inorganic fillers in the photosensitive resin composition is converted to solid content, for 100 parts by mass of the carboxyl group-containing resin, it is preferably 1 to 500 parts by mass, and 10 to 300 parts by mass. Is better. This makes it possible to further increase the adhesion reduction resistance of the photosensitive resin composition and the resistance to cold and heat cycles.
In addition, from the viewpoints of the reduction in the adhesion of the photosensitive resin composition and the prevention of cold and heat cycles, the compounding amount of barium sulfate in the photosensitive resin composition is 100 masses for the carboxyl group-containing resin in terms of solid content. In terms of parts, 50 parts by mass or less is preferred, 10 parts by mass or less is preferred, and those not contained are particularly preferred.

When the photosensitive resin composition contains spherical silica and alumina, the content ratio with talc and mica (the sum of the contents of talc and mica: spherical silica: alumina) is based on the mass standard, It is preferably 1: 0.1 to 99: 0.1 to 99, and more preferably 1: 0.1 to 9: 0.1 to 9. This can further improve the heat resistance and cold-heat cycle resistance of the photosensitive resin composition.

[(7) Bi-functional (meth) acrylates without isocyanuric ring]
It is preferable that the photosensitive resin composition of this invention contains the bifunctional or more (meth) acrylate which does not have an isocyanuric acid ring. This makes it possible to further improve the heat resistance and the cold-heat cycle resistance of the photosensitive resin composition.

Examples of bifunctional or more (meth) acrylates which do not have an isotricyanic acid ring include trimethylolpropane tri (meth) acrylate and ethoxylated trimethylolpropane. Tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (methyl) Acrylate), ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these caprolactone modifications.
A bifunctional or more (meth) acrylate which does not have an isocyanuric acid ring may be used individually by 1 type, and may be used in combination of 2 or more type.

When the blending amount of the bifunctional or more (meth) acrylic acid ester which does not have an isocyanuric ring in the photosensitive resin composition is converted to solid content, it is 1 to 100 parts by mass of the carboxyl group-containing resin. It is preferably 50 parts by mass, and more preferably 10 to 50 parts by mass. This makes it possible to further improve the heat resistance and the cold-heat cycle resistance of the photosensitive resin composition.

[(8) Colorant]
A coloring agent may be contained in the photosensitive resin composition. As the colorant, known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments can be used. However, from the standpoint of reducing the environmental load and the impact on the human body, those who do not contain halogen are preferred.

As the red colorant, there are monoazo-based, disazo-based, azo dye-based, benzimidazolone-based, fluorene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, and quinacridone Departments and the like specifically include those with a color index (CI; issued by The Society of Dyers and Colourists) number as shown below.

Examples of the monoazo-based red colorant include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. Examples of the disazo red colorant include Pigment Red 37, 38, and 41. Examples of the monoazo dye-based red colorant include Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52 : 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68, and so on. Examples of the benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, and 208. Examples of the actinic red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. Examples of the diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, and 272. Examples of the condensed azo-based red colorant include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of the anthraquinone-based red colorants include Pigment Red 168, 177, and 216, Solvent Red 149, 150, 52, and 207.
Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, and 209.

Examples of the blue colorant include phthalocyanine and anthraquinone. Pigments include compounds classified as pigments. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. As the dye system, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinoline-based, and anthraquinone-based. For example, as the anthraquinone-based yellow colorant, Examples include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, and the like. Examples of the isoindoline-based yellow colorant include Pigment Yellow 110, 109, 139, 179, and 185. Examples of the condensed azo-based yellow colorant include Pigment Yellow
93, 94, 95, 128, 155, 166, 180, etc. Examples of the benzimidazolone-based yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181. Examples of the monoazo-based yellow colorant include Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Examples of the disazo yellow colorant include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc.

Other colorants such as purple, orange, brown, black, and white can also be added. Specific examples include Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29 , 32, 36, 38, 42, Solvent Violet 13, 36, CIPigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63 , 64, 71, 73, Pigment Brown 23, 25, carbon black, titanium oxide, etc.

The content of the coloring agent in the photosensitive resin composition is not particularly limited, but in terms of solid content, it is preferably set to 0.1 to 3 parts by mass for 100 parts by mass of the carboxyl group-containing resin. However, when the content of the white colorant such as titanium oxide is converted to solid content, it is preferably 0.1 to 200 parts by mass for 100 parts by mass of the carboxyl group-containing resin.

[(9) Organic solvents]
The photosensitive resin composition of the present invention may contain an organic solvent, whereby viscosity can be adjusted.
The usable organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. . More specific examples include ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methylcellosolve, butylcellosolve, Glycol ethers such as carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate (carbitol acetate), dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether ethyl Esters such as acid esters, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane, decane; petroleum ether, naphtha, hydrogenated naphtha, Petroleum solvents such as solvent naphtha. Such organic solvents may be used alone or as a mixture of two or more.

Volatile drying of organic solvents can be achieved by using a hot-air circulation type drying furnace, IR furnace, heating plate, convection oven, etc. By spraying a support from a nozzle).

The content of the organic solvent in the photosensitive resin composition may be appropriately changed according to the material constituting the photosensitive resin composition. For example, when the solid content is converted, the content is set to 10 for 100 parts by mass of the carboxyl group-containing resin. ～ 1000 parts by mass are preferred.

[Photosensitive resin composition in the second aspect]
In the second aspect, the photosensitive resin composition is a two-liquid type photosensitive resin composition composed of the first composition and the second composition. The "two-liquid photosensitive resin composition" in the present invention means a combination of the first composition and the second composition, that is, the former of the mixture of these compositions.
Since the photosensitive resin composition has a two-liquid type as described above, the adhesion of the photosensitive resin composition can be prevented from lowering, and the resistance to cold and heat cycles can be made better.
In addition, when the two-liquid type photosensitive resin composition is used, it is preferable to mix the first composition and the second composition and stir until they are uniform before using.

[First composition]
The first composition contains at least a carboxyl group-containing resin and a photopolymerization initiator.
The first composition preferably contains at least one of talc and mica. Since the first composition contains at least one of talc and mica, the cold-heat cycle resistance of the photosensitive resin composition can be further improved.
The first composition is a (meth) acrylic acid ester which may contain a bifunctional or more functional group having an isocyanuric ring.
The first composition preferably contains another inorganic filler. Since the first composition contains other inorganic fillers, the cold-heat cycle resistance of the photosensitive resin composition can be further improved.
The first composition is preferably one containing a bifunctional or higher (meth) acrylate which does not have an isocyanuric ring. The first composition is a (meth) acrylic acid ester containing a bifunctional or more functional group which does not have an isocyanuric ring, so that the heat resistance of the photosensitive resin composition can be further improved.
The first composition may contain at least one of a colorant and an organic solvent.
Specific examples of these constituent materials are as described above, and when the content is a mixture of the first composition and the second composition, the content is preferably the content described above.

[Second composition]
The second composition contains at least an epoxy resin.
The second composition may contain at least one of talc and mica.
Moreover, it is preferable that the 2nd composition contains the bifunctional or more (meth) acrylate which has an isocyanuric acid ring. Since the second composition contains a bifunctional or higher (meth) acrylate having an isotricyanate ring, the cold-heat cycle resistance of the photosensitive resin composition can be further improved.
The second composition may contain other inorganic fillers.
In addition, the second composition may contain a bifunctional or higher (meth) acrylate which does not have an isocyanuric ring.
The second composition may contain at least one of a colorant and an organic solvent.
Specific examples of these constituent materials are as described above. When the content is mixed with the first composition and the second composition, the content is preferably the content described above.

The reason why the (meth) acrylic acid ester having an isotricyanate ring is contained in the second composition as the inorganic filler in the first composition is not clear, but it is estimated as follows Show.
That is, it is considered that the compatibility between the epoxy resin and the (meth) acrylate having an isotricyanate ring is good, and that the (meth) acrylate having an isotricyanate ring can be sufficiently dispersed. . On the other hand, it is considered that an inorganic filler is contained in a composition having a carboxyl group-containing resin, and the compatibility with an organic component is compared with a (meth) acrylic acid ester containing an isotricyanate ring. A carboxyl resin is preferred because it can be sufficiently dispersed during curing. However, this is only a speculative range and is not necessarily limited to this.

[use]
The photosensitive resin composition of the present invention is particularly suitable for a printed wiring board when forming a cured film, and can be used as a solder resist layer, an interlayer insulating material, a marking ink, a cover film, a soldering dam, and a printed wiring board. The through hole of the perforation or through hole or the hole portion of the recess is used as a filler for burying a hole. Among these, it is also preferable to be used for forming a solder resist layer.

[Dry film]
The dry film of the present invention is a resin layer provided with a film and the above-mentioned photosensitive resin composition or the above-mentioned two-liquid type photosensitive resin composition mixed and stirred.
The dry film may include a protective film on the resin layer.

Although the material of the film and the protective film is not particularly limited, for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyimide can be used. , Copper foil, aluminum foil, etc. A surface treatment such as a corona treatment is preferably applied to the surface of these films. Thereby, the adhesiveness with a resin layer can be improved.

Although the thickness of a film and a protective film is not specifically limited, For example, it can be 5 micrometers-50 micrometers.

The dry film can be produced by coating and drying the photosensitive resin composition or the two-liquid type photosensitive resin composition mixed and stirred on the film by a conventionally known method such as a screen printing method. . The drying method is also not particularly limited, and can be performed by using a hot-air circulation type drying furnace or the like.

[Printed wiring board]
The printed wiring board of this invention has a hardened | cured material formed by the said photosensitive resin composition or the said two-liquid type photosensitive resin composition or the resin layer of the said dry film which were mixed and stirred.

As the printed wiring board of the present invention, for example, the curable resin composition of the present invention can be adjusted to a viscosity suitable for a coating method by using the organic solvent, and the substrate can be subjected to a dip coating method, a flow coating method, or a roll coating method. After coating with a method such as rod coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ° C, and then it is formed to be non-sticky. Sexual resin layer. In the case of a dry film, a resin layer and a substrate are bonded to the substrate with a laminate or the like, and then the resin film is formed on the substrate by peeling the carrier film.

Examples of the substrate include a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance by copper or the like. Other examples include paper phenol, epoxy paper, epoxy glass cloth, and glass polymer. For imine, glass cloth / epoxy nonwoven cloth, glass cloth / epoxy paper, epoxy synthetic fiber, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. Copper-clad laminates of all grades (FR-4, etc.) made of copper-clad laminates. Other examples include metal substrates, polyimide films, polyethylene terephthalate films, and polyethylene naphthalate. Ester (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.

The volatilization drying after coating the curable resin composition of the present invention can be performed by using a hot-air circulation drying oven, an IR oven, a heating plate, a convection oven, etc. (a person using a heat source having an air heating method by steam , The method of making hot air in the dryer to make countercurrent contact and the method of spraying the support by a nozzle).

After the resin layer is formed on the substrate, a mask having a predetermined pattern is formed, and exposure is performed by selective active energy rays, and the unexposed portion is exposed to a dilute alkali aqueous solution (for example, a 0.3 to 3% by mass aqueous soda carbonate solution). ) Development is performed to form a pattern of the hardened material. Further, the hardened material is irradiated with active energy rays, and then heat-cured (for example, 100 to 220 ° C), or after heat curing, the active energy rays are irradiated, or the final hardening (mainly hardening) is completed only by heat curing, and then Forms a hardened film with excellent properties such as adhesion and hardness.

As an exposure machine used for the above-mentioned active energy ray irradiation, a device capable of irradiating ultraviolet rays in a range of 350 to 450 nm may be installed as a high-pressure mercury light lamp, ultra-high pressure mercury light lamp, metal halide lamp, mercury short-arc lamp, etc. It is also possible to use a direct drawing device (for example, a laser direct imaging device that draws an image in a direct laser manner through CAD data of a computer). As the light source or laser light source of the direct scan machine, the maximum wavelength can be in the range of 350 ~ 450nm. Although the amount of exposure to be imaged varies depending on the film thickness, etc., it is generally 10 to 1000 mJ / cm ² , and it is preferably set within a range of 20 to 800 mJ / cm ² .

As the above-mentioned development method, a dipping method, a spray method, a spray method, a brushing method, or the like can be used, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate can be used. , Ammonia, amines and other alkaline aqueous solutions.

[Example]

Examples are given next to describe the present invention in more detail, but the present invention is not limited to these examples.

<Synthesis example: Preparation of carboxyl-containing resin paint A>
220 mass parts (1 equivalent) of cresol novolac epoxy resin (EOCN-104S manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220 g / eq), 140.1 mass parts of carbitol acetate, and solvent stone 60.3 parts by mass of naphtha was added to a flask, and dissolved by heating and stirring at 90 ° C. Once the obtained solution was cooled to 60 ° C, 72 parts by mass of acrylic acid (1 mole), 0.5 parts by mass of methylhydroquinone, and 2 parts by mass of triphenylphosphine were added, and the mixture was heated at 100 ° C for about 12 hours. The reaction yielded a reactant having an acid value of 0.2 mgKOH / g. 80.6 parts by mass (0.53 moles) of tetrahydrophthalic anhydride was added here, and the mixture was heated at 90 ° C for about 6 hours to obtain a resin having a solid content concentration of 65.8% and a solid content acid value of 85 mgKOH / g. Solution. This is hereinafter referred to as carboxyl-containing resin paint A.

<Synthesis example: Preparation of carboxyl-containing resin paint B>
380 parts by mass of a bisphenol F-type epoxy resin with X being CH ₂ and an average degree of polymerization n of 6.2 in the following general formula (1) and 925 parts by mass of epichlorohydrin were dissolved in dimethyl sulfene 462.5 After stirring, 98.5% NaOH 60.9 parts by mass (1.5 mol) was added at 70 ° C over 100 minutes with stirring. After the addition, the reaction was further performed at 70 ° C for 3 hours.

After the reaction was completed, 250 parts by mass of water was added and washed with water. After oil-water separation, from the oil layer, most of the dimethyl sulfene and excess unreacted epichlorohydrin are distilled and recovered under reduced pressure, and the reaction product containing the residual by-product salt and dimethyl sulfene is recovered. It was dissolved in 750 parts by mass of methyl isobutyl ketone, 10 parts by mass of 30% NaOH was added, and the reaction was performed at 70 ° C. for 1 hour.
After completion of the reaction, washing was performed twice with 200 parts by mass of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain epoxy resin (a) having an epoxy equivalent weight of 310 g / eq and a softening point of 69 ° C.
When the obtained epoxy resin (a) is calculated from an epoxy equivalent, it is about 5 of 6.2 of the alcoholic hydroxyl groups in the aforementioned starting material bisphenol F-type epoxy resin being epoxidized. 310 parts by mass of the epoxy resin (a) and 282 parts by mass of carbitol acetate were placed in a flask, and the mixture was dissolved by heating and stirring at 90 ° C.
Once the obtained solution was cooled to 60 ° C, 72 parts by mass of acrylic acid (1 mole), 0.5 parts by mass of methylhydroquinone, and 2 parts by mass of triphenylphosphine were added, and the reaction was heated at 100 ° C for about 60 hours to obtain The reactant had an acid value of 0.2 mgKOH / g. Here, 140 parts by mass (0.92 mol) of tetrahydrophthalic anhydride was added, and the mixture was heated at 90 ° C. to react until the acid value of the solid content was 100 mgKOH / g to obtain a resin solution having a solid content concentration of 65%. This is hereinafter referred to as carboxyl-containing resin paint B.

<Synthesis example: Preparation of carboxyl-containing resin paint C>
380 parts by mass of a bisphenol A type epoxy resin in which X in the general formula (1) is C (CH ₃ ) ₂ and an average polymerization degree n is 6.2, and 925 parts by mass of epichlorohydrin are dissolved in dimethyl After 462.5 parts by mass of fluorene, 98.5% by mass of NaOH (1.5 mol) was added at 70 ° C over 100 minutes with stirring. After the addition, the reaction was further performed at 70 ° C for 3 hours.
After the reaction was completed, 250 parts by mass of water was added and washed with water. After oil-water separation, from the oil layer, most of the dimethyl sulfene and excess unreacted epichlorohydrin were distilled and recovered under reduced pressure, and the reaction product containing the residual by-product salt and dimethyl sulfene was dissolved. To 750 parts by mass of methyl isobutyl ketone, 10 parts by mass of 30% NaOH was further added, and a reaction was performed at 70 ° C. for 1 hour.
After completion of the reaction, washing was performed twice with 200 parts by mass of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy equivalent (310 g / eq) and an epoxy resin (a) having a softening point of 69 ° C.
When the obtained epoxy resin (a) was calculated from an epoxy equivalent, it was about 5 of 6.2 of the alcoholic hydroxyl groups in the aforementioned starting material bisphenol F-type epoxy resin being epoxidized. 310 parts by mass of the epoxy resin (a) and 282 parts by mass of carbitol acetate were added to a flask, and the mixture was dissolved by heating and stirring at 90 ° C.
Once the obtained solution was cooled to 60 ° C, 72 parts by mass of acrylic acid (1 mole), 0.5 parts by mass of methylhydroquinone, and 2 parts by mass of triphenylphosphine were added, and the reaction was heated at 100 ° C for about 60 hours to obtain The reactant had an acid value of 0.2 mgKOH / g.
Here, 140 parts by mass (0.92 mol) of tetrahydrophthalic anhydride was added, and the mixture was heated at 90 ° C. and reacted until the acid value of the solid content was 100 mgKOH / g to obtain a resin solution having a solid content concentration of 65%. Hereinafter referred to as carboxyl-containing resin paint C.

<Synthesis example: Preparation of carboxyl-containing resin paint D>
In a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen substitution, and a stirrer, 42 parts by mass of methacrylate, 43 parts by mass of methmethacrylate, 35 parts by mass of styrene, and benzyl 35 parts by mass of acrylate, 100 parts by mass of carbitol acetate, 0.5 parts by mass of lauryl mercaptan, and 4 parts by mass of azobisisobutyronitrile were heated at 75 ° C for 5 hours under a nitrogen stream to carry out a polymerization reaction to obtain Copolymer solution (solid content concentration: 50 parts by mass).
Here, 0.05 parts by mass of hydroquinone, 23 parts by mass of glycidyl methacrylate, and 2.0 parts by mass of dimethylbenzylamine were added, and the addition reaction was performed at 80 ° C for 24 hours, and then carbitol acetic acid was added. 35 parts by mass of the ester, a copolymerized resin solution having an aromatic ring having a solid content concentration of 50% by mass was obtained. This is hereinafter referred to as carboxyl-containing resin paint D.

Example 1-1
<Preparation of photosensitive resin composition>
The carboxyl-containing resin paint A obtained as described above, LMP-100 talc manufactured by Fuji Talc Co., Ltd., and ethoxylated isocyanate as a bifunctional or more (meth) acrylate compound having an isotricyanic acid ring Cyanuric acid triacrylate (A9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd.), cresol novolac type epoxy resin (N-695 manufactured by DIC Corporation) and phenol as a thermosetting epoxy resin Novolac epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd.), Omnirad 907 manufactured by IGM Resins as a photopolymerization initiator, DETX-S manufactured by Nippon Kayaku Co., Ltd., and Datong Chemical Industry Co., Ltd. EAB manufactured by the company, crystalline silicon dioxide (Imsil A8, manufactured by Unimin Corporation) as other inorganic fillers, and dipentaerythritol hexahexamethylene dimethacrylate as a bifunctional or higher-functional (meth) acrylate compound having no isocyanuric ring Acrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), FASTOGEN GREEN S, manufactured by DIC Co., Ltd., as a colorant, and carbitol acetate, an organic solvent, and petroleum solvents (Showa Chemical Industries, Ltd.) Co., Ltd. of SOLVESSO150) after deployment at a ratio (parts by mass) as shown in Table 1, to the mixer for preliminary mixing, three roll mixer to prepare a photosensitive resin composition after kneading.

Examples 1-2 to 1-12 and Comparative Examples 1-1 to 1-3
The photosensitive resin composition was prepared in the same manner as in Example 1-1 except that the composition of the photosensitive resin composition was changed to that described in Table 1.

The details of each component in Table 1 are shown below.
(1) Resin lacquers A to D containing carboxyl groups (all are used as the amount of paint)
(2) Talc LMP-100 Talc: manufactured by Fuji Talc Co., Ltd.
(3) Bi- or more-functional (meth) acrylate with isocyanuric acid ring 聚 A9300: manufactured by Shin Nakamura Chemical Industry Co., Ltd., ethoxylated isocyanurate tri (meth) acrylate ･ A9300 -CL: manufactured by Shin Nakamura Chemical Industry Co., Ltd., caprolactone-modified ethoxylated isocyanurate tri (meth) acrylate ･ M-215: manufactured by Toa Synthesis Co., Ltd., ethoxylated isocyanate Uric acid di (meth) acrylate
(4) Epoxy resin N695: cresol novolac epoxy resin manufactured by DIC Co., Ltd. RE-306: phenol novolac epoxy resin manufactured by Nippon Kayaku Co., Ltd. jER834: Mitsubishi Chemical Corporation Limited TEPIC-S, a bisphenol A epoxy resin manufactured by the company: Triazine ring epoxy resin, manufactured by Nissan Chemical Industries, Ltd.
(5) Photopolymerization initiator ･ Omnirad 907: manufactured by IGM Resins, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-acetone ･ Omnirad TPO: Kaya Cure DETX-S manufactured by IGM Resins, 2,4,6-trimethylbenzylidene diphenylphosphine oxide: 2,4-diethylthioxanthone produced by Nippon Kayaku Co., Ltd. ･ EAB: manufactured by Datong Chemical Industry Co., Ltd., 4,4'-diethylaminobenzophenone
(6) Other inorganic fillers: Imsil A8: crystalline silica made by Unimin Corporation; Adma fineSO-C5: Admatechs Co., Ltd., spherical silica; A-26: made by Sumitomo Chemical Co., Ltd., Alumina ･ B-30: made by 堺 Chem Industry Co., Ltd., barium sulfate
(7) Bi- or more-functional (meth) acrylates without isocyanuric acid ring ･ Kaya Cure DPHA: manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexa (meth) acrylate ･ M-350: East Asia Synthetic Co., Ltd., ethoxylated trimethylolpropane tri (meth) acrylate
(8) Colorant ･ FASTOGEN GREEN S: manufactured by DIC Corporation
(9) Organic solvent VSOLVESSO150: manufactured by Showa Chemical Industry Co., Ltd.

Example 2-1
<Preparation of two-liquid type photosensitive resin composition>
Paint the carboxyl group-containing resin A obtained as described above, LMP-100 talc manufactured by Fuji Talc Co., Ltd., Omnirad 907 manufactured by IGM Resins Corporation as a photopolymerization initiator, and DETX- manufactured by Nippon Kayaku Co., Ltd. S and EAB manufactured by Datong Chemical Industry Co., Ltd., crystalline silicon dioxide (Imsil A8 manufactured by Unimin Corporation) as other inorganic fillers, and bifunctional or more (methyl ) Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.), FASTOGEN GREEN S manufactured by DIC Corporation as a colorant, carbitol acetate as an organic solvent, and petroleum The solvent (SOLVESSO150 manufactured by Showa Chemical Industry Co., Ltd.) was prepared in the proportion (parts by mass) shown in Table 2 below, premixed with a mixer, and kneaded with a three-roller mixer to prepare a first composition.
An ethoxylated isocyanurate triacrylate (A9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as a bifunctional or more functional (meth) acrylate compound having an isotricyanate ring, and thermosetting property Ingredients of cresol novolac epoxy resin (N-695 manufactured by DIC) and phenol novolac epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd.), and organic Solvent carbitol acetate and petroleum-based solvents (SOLVESSO150 manufactured by Showa Chemical Industry Co., Ltd. are prepared in the proportion (parts by mass) shown in Table 2 below, premixed with a mixer, and then mixed with three rollers. After kneading, a second composition was prepared, and a two-liquid photosensitive resin composition composed of the first composition and the second composition was obtained.
Thereafter, the first composition and the second composition are mixed and stirred until uniform.

Examples 2-2 to 2-14 and Comparative Examples 2-1 to 2-3
The two-component photosensitive resin composition was prepared in the same manner as in Example 2-1 except that the composition changes of the first composition and the second composition were as described in Table 2. Thereafter, the first composition and the second composition are mixed and stirred until uniform.

Example 3-1
<Preparation of photosensitive resin composition>
Paint the carboxyl group-containing resin A obtained as described above, synthetic mica MK-100 manufactured by Katakura Coop Agri Co., Ltd., and ethoxylate as a bifunctional or more (meth) acrylate compound having an isotricyanic acid ring. N-isocyanuric acid triacrylate (A9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd.), a cresol novolac epoxy resin (N-695 manufactured by DIC Corporation) as an epoxy resin which is a thermosetting component ), Omnirad TPO manufactured by IGM Resins as a photopolymerization initiator, DETX-S manufactured by Nippon Kayakusho Co., Ltd., and spherical silica (Adma fineSO-made by Admatechs Co., Ltd.) as other inorganic fillers. C5), dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) as a bifunctional or more (meth) acrylate compound having no isocyanuric acid ring, and DIC Corporation as a colorant FASTOGEN GREEN S was prepared and blended with carbitol acetate as an organic solvent in the proportion (parts by mass) shown in Table 1 below. After preliminary mixing with a stirrer, kneading was performed with a three-roller mixer to prepare a feeling. Resin composition.

Examples 3-2 to 3-7 and Comparative Examples 3-1 to 3-3
The photosensitive resin composition was prepared in the same manner as in Example 3-1 except that the composition of the photosensitive resin composition was changed to that described in Table 3.

The details of each component in Table 3 are shown below. In addition, description is omitted for those overlapping with Table 1.
(2) Mica osmium MK-100: made by Katakura Coop Agri Co., Ltd., synthetic mica, KAl ₂ (AlSi ₃ O ₁₀ ) F ₂ , average particle size 3.4 μm
･ M-HF: made by Repko Co., Ltd., natural mica, KAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ , average particle size 4 μm

Example 4-1
<Preparation of two-liquid type photosensitive resin composition>
Paint the carboxyl group-containing resin A obtained as described above, MK-100 mica manufactured by Katakura Coop Agri Co., Ltd., Omnirad TPO manufactured by IGM Resins Corporation as a photopolymerization initiator, and DETX- manufactured by Nippon Kayaku Co., Ltd. S. Spherical silicon dioxide (AdmafineSO-C5, manufactured by Admatechs Co., Ltd.) as other inorganic fillers, and dipentaerythritol as a bifunctional or more (meth) acrylate compound having no isocyanuric ring Hexacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.), FASTOGEN GREEN S manufactured by DIC Co., Ltd. as a colorant, and carbitol acetate as an organic solvent are used in the proportion shown in Table 4 below (parts by mass) ) Is prepared, pre-mixed in a blender, and kneaded with a three-roller mixer to prepare a first composition.
An ethoxylated isocyanurate triacrylate (A9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as a bifunctional or more (meth) acrylate compound having an isotricyanate ring, and thermosetting property The cresol novolac type epoxy resin (N-695 manufactured by DIC Co., Ltd.) and the carbitol acetate as an organic solvent are blended in the proportions (parts by mass) shown in Table 4 below. After premixing with a blender, knead with a three-roller mixer to prepare a second composition. A two-component photosensitive resin composition obtained from the first composition and the second composition was obtained.
Thereafter, the first composition and the second composition are mixed and stirred until uniform.

＜ Production of Evaluation Board ＞
Each resin composition obtained from the above Examples and Comparative Examples (for Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-3, Examples 4-1 to 4-9, and Comparative Example 4-1 ～ 4-3 are the mixture of the first resin composition and the second resin composition). It is screen-printed and fully coated on a circuit pattern substrate with a copper thickness of 35 μm, dried at 80 ° C for 30 minutes, and cooled to room temperature. A resin layer having a thickness of 20 μm was formed. For the resin layer, an exposure device equipped with a high-pressure mercury lamp (short arc lamp) was used to perform solid exposure at an optimum exposure amount, and then a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 60 seconds under a spray pressure of 0.2 MPa.
For the substrate, under a condition of a cumulative exposure amount of 1000 mJ / cm ² in a UV conveying furnace, the resin layer was hardened after being irradiated with ultraviolet rays and then heated at 160 ° C. for 60 minutes.

＜ Solder heat resistance ＞
The rosin-based flux was applied to the evaluation substrate prepared as described above, and then immersed twice in a solder bath at 260 ° C. for 30 seconds. Next, the appearance of the flux after washing with the modified alcohol was visually observed, and evaluated based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4.
(Evaluation criteria)
(Circle): Even if it immersed in a solder bath, peeling of the hardened resin layer was not observed.
Δ: After the dipping in the solder bath, peeling of the cured resin layer was slightly observed.
×: After immersion in the solder bath, significant peeling of the cured resin layer was observed.

＜ Cold and hot cycle resistance ＞
On the substrate forming the copper wire pattern of 2 mm, each resin composition obtained from the above examples and comparative examples was fully coated by screen printing, dried at 80 ° C for 30 minutes, and then cooled to room temperature to form a film. Evaluation board for 17 resist patterns of 3mm square.
This evaluation substrate was placed in a cold-heat cycler that was temperature cycled between -65 ° C and 150 ° C, and TCT (Thermal Cycle Test) was performed. Then, the appearance at 1,000 cycles was observed, the number of cracks was counted, and evaluation was performed according to the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4. And the denominator value "68" means 4 angles (4) x 17 angles of 68 in a 3mm square resist pattern, and the value of the numerator "30" etc. indicates the number of cracks.
(Evaluation criteria)
◎: 20/68 or less ○: 21/68 or more and 30/68 or less △: 31/68 or more and 40/68 or less ×: 41/68 or more

＜ Preventive adhesion reduction ＞
The evaluation substrate produced as described above was heated at 150 ° C. for 2,000 hours using a hot air circulation drying oven DN610 manufactured by Yamato Scientific Co., Ltd. Thereafter, 100 square scratches of 1 mm ² square were performed on each evaluation substrate using an automatic cross-cut tester No. 807-KS2 manufactured by Coating Tester Co., Ltd. Thereafter, peeling of the resin layer was confirmed by peeling the tape, and evaluation was performed according to the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4.
(Evaluation criteria)
◎: Peeling, no defect 0: Peeling, the number of defects is 1 or more and 15 or less △: Peeling, the number of defects is more than 15 and less than 35 ×: Peeling, the number of defects is more than 35 and 65 The following ××: There are flaking, and the number of defects exceeds 65

As can be seen from the examples, the photosensitive resin composition of the present invention can significantly improve any of heat resistance, prevention of adhesion reduction, and resistance to cold and heat cycles.
Further, it was found that when the photosensitive resin composition is used as a two-liquid type, it is possible to further reduce the prevention of adhesion and the resistance to cold and heat cycles.

Claims (12)

A photosensitive resin composition, comprising: Carboxyl group resin At least one of talc and mica; (Meth) acrylic acid ester having more than two functions of isocyanuric acid ring; Epoxy resin; and Photopolymerization initiator. The photosensitive resin composition according to claim 1, wherein at least one of a novolak-type carboxyl-containing resin and a bisphenol-type carboxyl-containing resin is contained as the carboxyl-containing resin. The photosensitive resin composition according to claim 1 or 2, which contains at least one of silicon oxide and aluminum oxide. The photosensitive resin composition according to any one of claims 1 to 3, which contains a (meth) acrylic acid ester having a bifunctional or higher function without an isotricyanic acid ring. The photosensitive resin composition according to any one of claims 1 to 4, which contains fluorine-containing mica as the mica. A two-liquid type photosensitive resin composition, which is a two-liquid type photosensitive resin composition composed of a first composition and a second composition, which is characterized by: The aforementioned first composition contains a carboxyl group-containing resin and a photopolymerization initiator; The second composition contains an epoxy resin; At least one of the first composition and the second composition contains at least one of talc and mica; and At least one of the first composition and the second composition contains a bifunctional or higher (meth) acrylate having an isotricyanate ring. According to claim 6bis, the liquid-type photosensitive resin composition, wherein the first composition contains at least one of talc and mica. The two-component photosensitive resin composition according to claim 6 or 7, wherein the second composition contains a (meth) acrylic acid ester having a bifunctional or higher function having an isotricyanic acid ring. The two-liquid photosensitive resin composition according to any one of claims 6 to 8, wherein the first composition contains at least one of silicon oxide and alumina. The two-component photosensitive resin composition according to any one of claims 6 to 9, wherein the first composition contains a bifunctional or higher (meth) acrylate having no isocyanuric ring. A dry film characterized by: Membrane; and The resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 5 or the two-component photosensitive resin composition according to any one of claims 6 to 10 to a film and drying it. A printed wiring board comprising a photosensitive resin composition according to any one of claims 1 to 5, a two-liquid type photosensitive resin composition according to any one of claims 6 to 10, or a request A cured product obtained by curing the resin layer of the dry film of 11