JP6759323B2 - Photosensitive resin composition, two-component photosensitive resin composition, dry film and printed wiring board - Google Patents

Description

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

Generally, in a printed wiring board used for an electronic device or the like, when mounting an electronic component on the printed wiring board, a connection on a substrate on which a circuit pattern is formed is formed in order to prevent solder from adhering to unnecessary parts. A solder resist layer is formed in the region other than the pores. Currently, the solder resist layer is made of a so-called photosolder resist, which is a cured product obtained by applying a photosensitive resin composition to a substrate, forming a pattern by exposure and development, and then main-curing the patterned resin by heating or light irradiation. It is mainly formed, and usually, such a photosensitive resin composition is required to have high solder heat resistance.

In recent years, the development of electric vehicles has progressed rapidly, and the above-mentioned substrate on which the solder resist layer is formed has been applied.
Such a power semiconductor for high power control for controlling an electric vehicle, a hybrid vehicle, a wind power generation device, or the like has a large amount of heat generation, and the substrate applied thereto is exposed to a high temperature environment for a long time. Therefore, in addition to heat resistance, the photosensitive resin composition is required to have a high adhesive force reduction preventive property in which the adhesive force does not decrease even in such a high temperature environment.
Further, such a power semiconductor has an extremely high temperature when energized and a low temperature when it is not energized, and this is repeated. Therefore, cracks are likely to occur in the solder resist layer, and the photosensitive resin composition has high thermal cycle resistance. Is required to have.

Here, Patent Document 1 proposes a photosensitive resin composition containing a photosensitive insulating resin, a thermosetting insulating resin, a polyfunctional acrylate having a triazine ring, and acrylonitrile butadiene, but the adhesive strength is prevented from decreasing. And there was room for improvement in thermal cycle resistance.

Further, in Patent Document 2, triglycidyl triisocyanurate is blended in a photosensitive resin composition for the purpose of improving heat resistance. However, in recent years, its use has been gradually withheld in consideration of environmental impacts such as mutagenesis.
Further, the cured product formed by using this photosensitive resin composition has a problem that it is inferior in cold cycle resistance. Therefore, there is a demand for a photosensitive composition having excellent heat resistance and cold cycle resistance.

Japanese Unexamined Patent Publication No. 2003-66603 Japanese Unexamined Patent Publication No. 9-185167

Therefore, an object of the present invention is to provide a photosensitive resin composition having high heat resistance, anti-adhesive strength reduction property, and cold cycle resistance. Another object of the present invention is to provide a dry film, a cured product, and a printed wiring board formed by using the photosensitive resin composition.

The photosensitive resin composition according to the present invention comprises a carboxyl group-containing resin, at least one of talc and mica, a bifunctional or higher functional (meth) acrylate having an isocyanul ring, an epoxy resin, and a photopolymerization initiator. It is characterized by including.

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

In the aspect of the present invention, it is preferable that the photosensitive resin composition 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 higher functional (meth) acrylate having no isocyanul ring.

In the aspect of the present invention, the photosensitive resin composition preferably contains fluorine-containing mica as mica.

The two-component curable photosensitive resin composition according to the present invention comprises a first composition and a second composition.
The first composition comprises a carboxyl group-containing resin and a photopolymerization initiator.
The second composition comprises an epoxy resin and
At least one of the first composition and the second composition comprises at least one of talc and mica.
At least one of the first composition and the second composition is characterized by containing a bifunctional or higher functional (meth) acrylate having an isocyanul ring.

In aspects of the invention, the first composition preferably comprises at least one of talc and mica.

In aspects of the invention, it is preferred that the second composition comprises a bifunctional or higher functional (meth) acrylate having an isocyanul ring.

In the aspect of the present invention, it is preferable that the first composition contains at least one of silicon oxide and aluminum oxide.

In aspects of the present invention, it is preferred that the first composition comprises a bifunctional or higher functional (meth) acrylate that does not have an isocyanul ring.

The dry film according to the present invention is characterized by having a film and a resin layer obtained by applying the photosensitive resin composition or the two-component photosensitive resin composition to the film and drying the film.

The printed wiring board according to the present invention is characterized in that it is obtained by curing the resin layer of the photosensitive resin composition, the two-component photosensitive resin composition, or the dry film.

According to the present invention, it is possible to provide a photosensitive resin composition having high heat resistance, anti-adhesion strength reduction property, and cold cycle resistance. Further, according to another aspect of the present invention, it is possible to provide a dry film, a cured product and a printed wiring board formed by using the photosensitive resin composition.

[Photosensitive resin composition in the first aspect]
In the first aspect, the photosensitive resin composition is photopolymerized with a carboxyl group-containing resin, at least one of talc and mica, a bifunctional or higher functional (meth) acrylate having an isocyanul ring, and an epoxy resin. Includes at least an initiator.
The photosensitive resin composition is composed of an inorganic filler other than talc and mica (hereinafter referred to as other inorganic filler), a bifunctional or higher functional (meth) acrylate having no isocyanul ring, a colorant and an organic solvent. At least one of them can be included.
Hereinafter, each component will be described in detail.

[(1) Carboxylic acid group-containing resin]
As the carboxyl group-containing resin, various conventionally known resins having a carboxyl group in the molecule can be used. When the photosensitive resin composition contains a carboxyl group-containing resin, alkali developability can be imparted to the photosensitive resin composition.
In particular, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.
When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, the composition can be prepared by using a (meth) acrylate having a bifunctional or higher functional (meth) acrylate having an isocyanul ring, which will be described later, in combination. It should be photosensitive.
Specific examples of the carboxyl group-containing resin include the following compounds (either oligomer or polymer).

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, or isobutylene.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing photosensitive urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(4) During the synthesis of the resin according to (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (4). Meta) Acryloylated carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin according to (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are formed in the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate isomorphic reaction product. A carboxyl group-containing photosensitive urethane resin that is terminally (meth) acrylicized by adding a compound to it.

(6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group existing in a side chain.

(7) Carboxylic acid obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl groups. Group-containing photosensitive resin.

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and the generated primary hydroxyl group is subjected to two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. A carboxyl group-containing polyester resin to which an acid anhydride is added.

(9) 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 (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing photosensitive resin obtained by reacting a polybasic anhydride such as an acid.

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

(11) Reaction obtained by reacting a reactive 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 or propylene carbonate by reacting an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

(12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (11).
In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to 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 40 mgKOH / g or more, alkaline development becomes good. Further, by setting the acid value to 150 mgKOH / g or less, it is possible to easily draw a good resist pattern. More preferably, it is 50 to 130 mgKOH / g.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, the developability and storage stability can be improved. More preferably, it is 5,000 to 100,000.

The blending amount of the carboxyl group-containing resin is preferably 20 to 60% by mass in terms of solid content in the photosensitive resin composition. The coating film strength can be improved by setting the content to 20% by mass or more. Further, when the content is 60% by mass or less, the viscosity becomes appropriate and the printability is improved. More preferably, it is 30 to 50% by mass.

[(2) Talc and mica]
The photosensitive resin composition contains at least one of talc and mica, which can improve the adhesion deterioration prevention property and the thermal cycle resistance of the photosensitive resin composition.

The average particle size (D50) of talc is preferably 0.1 μm to 100 μm, and more preferably 1 μm to 50 μm. By keeping the particle size within the above range, the dispersibility of talc in the photosensitive resin composition can be further improved.
Here, D50 is a particle size at a volume accumulation of 50% obtained by using a laser diffraction scattering type particle size distribution measurement method based on the Mie scattering theory. More specifically, it can be measured by producing a particle size distribution of fine particles on a volume basis by a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, those in which fine particles are dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, LA-500 manufactured by HORIBA, Ltd. or the like can be used.

The blending amount of talc in the photosensitive resin composition is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. .. Thereby, the adhesive force reduction prevention property and the thermal cycle resistance of the photosensitive resin composition can be further improved.

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

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

The blending amount of mica in the photosensitive resin composition is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. .. This makes it possible to further improve the heat resistance of the photosensitive resin composition, the ability to prevent a decrease in adhesion, and the resistance to cold cycle.

[(3) Bifunctional or higher functional (meth) acrylate having an isocyanul ring]
The photosensitive resin composition contains a bifunctional or higher functional (meth) acrylate having an isocyanul ring, whereby the heat resistance of the photosensitive resin composition, the resistance to decrease in adhesion, and the resistance to cold cycle can be improved.

Bifunctional or higher functional (meth) acrylates having an isocyanuric ring that can be used include, for example, ethoxylated isocyanuric acid di (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, and propoxylated isocyanuric acid di (meth) acrylate. ) Acrylate, tri (meth) acrylate of propoxylated isocyanuric acid and modified caprolactones thereof.

The blending amount of the bifunctional or higher functional (meth) acrylate having an isocyanul ring in the photosensitive resin composition is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. , 5 to 40 parts by mass, more preferably. This makes it possible to further improve the heat resistance of the photosensitive resin composition, the ability to prevent a decrease in adhesion, and the resistance to cold cycle.

[(4) Epoxy resin]
Examples of the epoxy resin that can be used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type epoxy. Examples thereof include resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and triphenylmethane type epoxy resins.
One of these epoxy resins may be used alone, or two or more of these epoxy resins may be used in combination.

Examples of commercially available epoxy resins include jER828, 806, 807, YX-8000, 8034, jER834 manufactured by Mitsubishi Chemical Corporation, and YD-128, YDF-170, ZX-1059 manufactured by Nippon Steel & Sumitomo Metal Corporation. Examples thereof include ST-3000, 830, 835, 840, 850, N-730A, N695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Corporation.

The equivalent of the epoxy group of the epoxy resin in the photosensitive resin composition is preferably 0.3 to 3.0 with respect to the equivalent of 1 of the carboxyl group of the carboxyl group-containing resin in terms of solid content. By setting the equivalent to 0.3 equivalent or more, it is possible to prevent residual carboxyl groups in the cured film and obtain good heat resistance, alkali resistance, electrical insulation and the like. On the other hand, by setting the above compounding amount to 3.0 equivalents or less, it is possible to prevent low molecular weight cyclic (thio) ether groups from remaining in the dry coating film and to ensure good strength of the cured film. it can.

[(5) Photopolymerization Initiator]
Examples of the photopolymerization initiator that can be used include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4). -Morholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N Α-Aminoacetophenone-based photopolymerization initiators such as −dimethylaminoacetophenone: 1-hydroxy-cyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-one Hydroxyacetophenone-based photopolymerization initiators such as methyl-1-phenylpropan-1-one; bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5- Dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-- Dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine Oxide, bis- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl Acylphosphine oxide-based photopolymerization initiators such as phenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Benzoyl, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-buchi Benzoine-based photopolymerization initiators such as ruether; benzoinalkylether-based photopolymerization initiators; benzophenones such as benzophenone, p-methylbenzophenone, Michelers ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone. Photopolymerization initiators; acetphenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone and other acetophenone-based photopolymerization initiators; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone , 2-Chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone-based photopolymerization initiators; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2- Anthraquinone-based photopolymerization initiators such as amylanthraquinone and 2-aminoanthraquinone; Ketal-based photopolymerization initiators such as acetophenone dimethyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p. -Anthraquinone ester-based photopolymerization initiators such as dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], anthraquinone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and other oxime ester-based photopolymerization initiators; bis (η5-2,4-cyclopentadiene) -1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2-yl) (1-Pill-1-yl) ethyl) phenyl] Titanosen-based photopolymerization initiators such as titanium; and the like.
As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

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

Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be preferably used, and specific examples thereof include an oxime ester compound having a carbazole structure represented by the following general formula.

In the above formula, X is 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 (alkyl groups having 1 to 17 carbon atoms, an alkoxy having 1 to 8 carbon atoms). Group, amino group, alkylamino group having 1 to 8 carbon atoms or dialkylamino group substituted), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, It is substituted with an amino group and an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), and Y and Z are a hydrogen atom, an alkyl group having 1 to 17 carbon atoms and 1 carbon atom, respectively. ~ 8 alkoxy groups, halogen groups, phenyl groups, phenyl groups (alkyl groups with 1 to 17 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, amino groups, alkyl amino groups having 1 to 8 carbon atoms or alkyl groups or Alkyl amino group or dialkyl amino having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms. Represents an anthryl group, pyridyl group, benzofuryl group, benzothienyl group), Ar represents an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, It represents furylene, 2,5-pyrrole-diyl, 4,4'-stilben-diyl, 4,2'-styrene-diyl, where n is an integer of 0 or 1.

In particular, in the above formula, it is preferable that X and Y are methyl groups or ethyl groups, respectively, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene.

In addition to the above-mentioned photopolymerization initiator, a benzoin compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, a xanthone compound and the like can be used as the photopolymerization initiator.
However, these are preferably used as a photopolymerization initiator or a sensitizer in combination with the above-mentioned photopolymerization initiator, rather than being used alone as a photopolymerization initiator.
Among the above, thioxanthone compounds and tertiary amine compounds are preferable, and thioxanthone compounds are more preferable, from the viewpoint of deep curability.
In addition, two or more of the above compounds may be used in combination.

The blending amount of the photopolymerization initiator in the photosensitive resin composition is preferably 1 to 50 parts by mass and 1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Is more preferable. Thereby, the curability of the deep part can be improved.
When the photosensitive resin composition contains the benzoin compound or the like as a photopolymerization initiator, the blending amount thereof is 0.01 to 10 to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is preferably parts by mass, more preferably 0.1 to 5 parts by mass.
Thereby, the curability of the deep part can be improved.

[(6) Other inorganic fillers]
The photosensitive resin composition according to the present invention preferably contains other inorganic fillers other than talc and mica. Thereby, the adhesive force reduction prevention property and the thermal cycle resistance of the photosensitive resin composition can be further improved.

Other inorganic fillers include silicon oxides such as amorphous silica, crystalline silica, molten silica and spherical silica, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, fly ash and dehydrated sludge. , Natural silica, synthetic silica, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate , Magnesium phosphate, Sepiolite, Zonolite, Boron nitride, Aluminum borate, Silica balloon, Glass flakes, Glass balloon, Silica, Iron slag, Copper, Iron, Iron oxide, Sendust, Alnico magnet, Magnetic powder such as various ferrites, Cement, Examples thereof include glass powder, Neuburg diatomaceous earth, diatomaceous earth, antimony trioxide, magnesium oxysulfate, aluminum hydrate, slag hydrate, myoban and barium sulfate. As for other inorganic fillers, one type may be used alone, or two or more types may be used in combination.
Among the above, it is preferable to contain at least one of silicon oxide and aluminum oxide, and further, by using two kinds of spherical silica and aluminum oxide in combination, the heat resistance and cold heat of the photosensitive resin composition can be obtained. It is more preferable because the cycle resistance is significantly improved.

The average particle size (D50) of the other inorganic filler is preferably 0.1 to 100 μm, more preferably 0.1 to 50 μm.

The blending amount of the other inorganic filler in the photosensitive resin composition is preferably 1 to 500 parts by mass and 10 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Is more preferable. This makes it possible to further improve the adhesive strength deterioration prevention property and the thermal cycle resistance of the photosensitive resin composition.
Further, from the viewpoint of preventing the adhesive strength of the photosensitive resin composition from decreasing and the resistance to the thermal cycle, the amount of barium sulfate blended in the photosensitive resin composition is based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably not contained.

When the photosensitive resin composition contains spherical silica and aluminum oxide, the content ratio of talc and mica (sum of talc and mica content: spherical silica: aluminum oxide) is 1: 0 on a mass basis. It is preferably 1 to 99: 0.1 to 99, and more preferably 1: 0.1 to 9: 0.1 to 9. Thereby, the heat resistance and the cold cycle resistance of the photosensitive resin composition can be further improved.

[(7) Bifunctional or higher functional (meth) acrylate without isocyanul ring]
The photosensitive resin composition according to the present invention preferably contains a bifunctional or higher functional (meth) acrylate having no isocyanul ring. Thereby, the heat resistance and the cold cycle resistance of the photosensitive resin composition can be further improved.

Examples of the bifunctional or higher functional (meth) acrylate that does not have an isocyanul ring that can be used include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri. (Meta) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylation 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. Examples thereof include propanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and modified caprolactones thereof.
As the bifunctional or higher functional (meth) acrylate having no isocyanul ring, one kind may be used alone, or two or more kinds may be used in combination.

The blending amount of the bifunctional or higher functional (meth) acrylate having no isocyanul ring in the photosensitive resin composition may be 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is preferably 10 to 50 parts by mass, more preferably. Thereby, the heat resistance and the cold cycle resistance of the photosensitive resin composition can be further improved.

[(8) Colorant]
The photosensitive resin composition may contain a colorant. As the colorant, known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable that it does not contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

Examples of the red colorant include monoazo type, disazo type, azolake type, benzimidazolone type, perylene type, diketopyrrolopyrrole type, condensed azo type, anthraquinone type, quinacridone type, and the like. -Index (CI; issued by The Society of Dyersand Colorists) numbered ones.

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

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

In addition, colorants such as purple, orange, brown, black, and white may be added. Specifically, 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, C.I. I. Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73, PigmentBrown 23,25, Carbon Black, Examples include titanium oxide.

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

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

Volatile drying of organic solvents is supported by hot air circulation type drying furnaces, IR furnaces, hot plates, convection ovens, etc. (using a steam-based air heating type heat source to bring hot air into the dryer into countercurrent contact and nozzles. It can be done by using the method of spraying on the body).

The content of the organic solvent in the photosensitive resin composition is preferably changed as appropriate according to the material constituting the photosensitive resin composition. For example, in terms of solid content, 10 is 10 parts by mass of the carboxyl group-containing resin. It can be ~ 1000 parts by mass.

[Photosensitive resin composition in the second aspect]
In the second aspect, the photosensitive resin composition is a two-component photosensitive resin composition comprising a first composition and a second composition. In the present invention, the "two-component photosensitive resin composition" refers to a combination of the first composition and the second composition, that is, a composition before mixing of these compositions.
As described above, by making the photosensitive resin composition a two-component type, it is possible to further improve the adhesive strength deterioration prevention property and the thermal cycle resistance of the photosensitive resin composition.
When the two-component photosensitive resin composition is used, it is preferable to mix the first composition and the second composition and stir until they become uniform before use.

[First composition]
The first composition contains at least a carboxyl group-containing resin and a photopolymerization initiator.
In addition, the first composition preferably contains at least one of talc and mica. By including at least one of talc and mica in the first composition, the thermal cycle resistance of the photosensitive resin composition can be further improved.
The first composition can also include a bifunctional or higher functional (meth) acrylate having an isocyanul ring.
In addition, the first composition preferably contains other inorganic fillers. By including the other inorganic filler in the first composition, the thermal cycle resistance of the photosensitive resin composition can be further improved.
In addition, the first composition preferably contains a bifunctional or higher functional (meth) acrylate having no isocyanul ring. When the first composition does not have an isocyanul ring and contains a bifunctional or higher functional (meth) acrylate, the heat resistance of the photosensitive resin composition can be further improved.
Furthermore, the first composition can contain at least one of a colorant and an organic solvent.
Specific examples of these constituent materials are as described above, and the content thereof is preferably the above-mentioned content when the first composition and the second composition are mixed.

[Second composition]
The second composition comprises at least an epoxy resin.
The second composition can also include at least one of talc and microphone.
In addition, the second composition preferably contains a bifunctional or higher functional (meth) acrylate having an isocyanul ring. When the second composition contains a bifunctional or higher functional (meth) acrylate having an isocyanul ring, the thermal cycle resistance of the photosensitive resin composition can be further improved.
In addition, the second composition may contain other inorganic fillers.
The second composition can also contain a bifunctional or higher functional (meth) acrylate that does not have an isocyanul ring.
Furthermore, the second composition can contain at least one of a colorant and an organic solvent.
Specific examples of these constituent materials are as described above, and the content thereof is preferably the above-mentioned content when the first composition and the second composition are mixed.

The reason why it is preferable that the inorganic filler has an isocyanul ring in the first composition and the (meth) acrylate is contained in the second composition is not necessarily clear, but is presumed as follows.
That is, it is considered that the (meth) acrylate having an epoxy resin and an isocyanul ring, having good compatibility with the (meth) acrylate and having a sufficient isocyanul ring, is dispersed. On the other hand, by including the inorganic filler in the composition containing the carboxyl group-containing resin, the carboxyl group-containing resin is better than the (meth) acrylate containing the isocyanul ring in terms of compatibility with the organic component, and when cured, it is better. This is probably because it is sufficiently dispersed. However, this is just a guess, and not necessarily this.

[Use]
The photosensitive resin composition according to the present invention is suitably used for forming a cured film particularly in a printed wiring board, and is used for forming a solder resist layer, an interlayer insulating material, a marking ink, a coverlay, a solder dam, and a through of a printed wiring board. It can be used as a filler for filling through holes and recessed holes in holes and via holes. Among these, it can be suitably used for forming a solder resist layer.

[Dry film]
The dry film of the present invention comprises a film and a resin layer formed of the above-mentioned photosensitive resin composition or the above-mentioned two-component photosensitive resin composition mixed and stirred.
Further, the dry film may be provided with a protective film on the resin layer.

The material of the film and the protective film is not particularly limited, and for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, copper foil, aluminum foil and the like can be used. .. It is preferable that the surface of these films is subjected to surface treatment such as corona treatment. Thereby, the adhesion with the resin layer can be improved.

The thickness of the film and the protective film is not particularly limited, but can be, for example, 5 μm to 50 μm.

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

[Printed circuit board]
The printed wiring board according to the present invention has the above-mentioned photosensitive resin composition or the above-mentioned two-component photosensitive resin composition mixed and stirred, or a cured product formed by the above-mentioned resin layer of the dry film.

As the printed wiring board according to the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above organic solvent, and a dip coating method or a flow coating method is applied onto the substrate. After coating by a roll coating method, a bar coater method, a screen printing method, a 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. A tack-free resin layer is formed. Further, in the case of a dry film, a resin layer is formed on the base material by sticking the resin layer on the base material with a laminator or the like so that the resin layer comes into contact with the base material and then peeling off the carrier film.

The base material includes a printed wiring board and a flexible printed wiring board whose circuit is formed of copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy. , Synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc. are used for high frequency circuit copper-clad laminates, etc., and all grades (FR-4, etc.) of copper-clad laminates are used. Plates, other metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

Volatile drying performed after applying the curable resin composition of the present invention is carried out in a hot air circulation type drying oven, IR furnace, hot plate, convection oven, etc. (using a steam-based air heating type heat source in the dryer). It can be carried out by using a method of bringing hot air into countercurrent contact and a method of blowing hot air onto a support from a nozzle).

After forming a resin layer on the substrate, it is selectively exposed to active energy rays through a photomask having a predetermined pattern, and the unexposed portion is exposed to a dilute alkaline aqueous solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution). To form a pattern of the cured product. Further, the cured product is adhered by irradiating the cured product with active energy rays and then heat-curing (for example, 100 to 220 ° C.), or by irradiating the cured product with active energy rays after heat curing, or by performing final finish curing (main curing) only by heat curing. It forms a cured film with excellent properties such as properties and hardness.

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

The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. Alkaline aqueous solutions such as ammonia and amines can be used.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Synthesis example: Preparation of carboxyl group-containing resin varnish A>
Flask with 220 parts by mass (1 equivalent) of cresol novolac type epoxy resin (EOCN-104S manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220 g / eq), 140.1 parts by mass of carbitol acetate, and 60.3 parts by mass of solvent naphtha. Was charged, heated to 90 ° C. and stirred to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts by mass (1 mol) of acrylic acid, 0.5 parts by mass of methylhydroquinone and 2 parts by mass of triphenylphosphine are added, heated to 100 ° C., and reacted for about 12 hours. , A reaction product having an acid value of 0.2 mgKOH / g was obtained. 80.6 parts by mass (0.53 mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ° C. and reacted for about 6 hours. A resin having a solid acid value of 85 mgKOH / g and a solid content concentration of 65.8%. A solution was obtained. Hereinafter, it is referred to as a carboxyl group-containing resin varnish A.

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

After completion of the reaction, 250 parts by mass of water was added and the mixture was washed with water. After oil-water separation, most of dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and the reaction product containing the residual by-salt and dimethyl sulfoxide was dissolved in 750 parts by mass of methyl isobutyl ketone, and further 30 parts were dissolved. 10 parts by mass of% NaOH was added, and the mixture was reacted at 70 ° C. for 1 hour.
After completion of the reaction, washing with 200 parts by mass of water was carried out twice. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 310 g / eq and a softening point of 69 ° C.
The obtained epoxy resin (a) was obtained by epoxidizing about 5 out of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin, calculated from the epoxy equivalent. 310 parts by mass of this epoxy resin (a) and 282 parts by mass of carbitol acetate were placed in a flask, heated and stirred at 90 ° C. to dissolve them.
The obtained solution is once cooled to 60 ° C., 72 parts by mass (1 mol) of acrylic acid, 0.5 parts by mass of methylhydroquinone and 2 parts by mass of triphenylphosphine are added, and the mixture is heated to 100 ° C. and reacted for about 60 hours. , A reaction product having an acid value of 0.2 mgKOH / g was obtained. 140 parts by mass (0.92 mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ° C. and reacted until the solid acid value reached 100 mgKOH / g to obtain a resin solution having a solid content concentration of 65%. .. Hereinafter, it is referred to as a carboxyl group-containing resin varnish B.

<Synthesis example: Preparation of carboxyl group-containing resin varnish C>
380 parts by mass of bisphenol A type epoxy resin in which X is C (CH ₃ ) ₂ and the average degree of polymerization n is 6.2 in the above general formula (1) and 925 parts by mass of epichlorohydrin are dimethyl sulfoxide 462.5 parts by mass. After dissolving in parts, 98.5% NaOH 60.9 parts by mass (1.5 mol) was added over 100 minutes at 70 ° C. with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours.
After completion of the reaction, 250 parts by mass of water was added and the mixture was washed with water. After oil-water separation, most of dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and the reaction product containing residual by-salt and dimethyl sulfoxide was dissolved in 750 parts by mass of methyl isobutyl ketone, and further 30%. 10 parts by mass of NaOH was added, and the mixture was reacted at 70 ° C. for 1 hour.
After completion of the reaction, washing with 200 parts by mass of water was carried out twice. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 310 g / eq and a softening point of 69 ° C.
The obtained epoxy resin (a) was obtained by epoxidizing about 5 out of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin, calculated from the epoxy equivalent. 310 parts by mass of the epoxy resin (a) and 282 parts by mass of carbitol acetate were placed in a flask, heated and stirred at 90 ° C. to dissolve them.
The obtained solution is once cooled to 60 ° C., 72 parts by mass (1 mol) of acrylic acid, 0.5 parts by mass of methylhydroquinone and 2 parts by mass of triphenylphosphine are added, and the mixture is heated to 100 ° C. and reacted for about 60 hours. , A reaction product having an acid value of 0.2 mgKOH / g was obtained.
140 parts by mass (0.92 mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ° C. and reacted until the solid acid value reached 100 mgKOH / g to obtain a resin solution having a solid content concentration of 65%. .. Hereinafter, it is referred to as a carboxyl group-containing resin varnish C.

<Synthesis example: Preparation of carboxyl group-containing resin varnish D>
42 parts by mass of methacrylic acid, 43 parts by mass of methyl methacrylate, 35 parts by mass of styrene, 35 parts by mass of benzyl acrylate, and carbitol acetate in a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen substitution, and a stirrer. 100 parts by mass, 0.5 parts by mass of lauryl mercaptan and 4 parts by mass of azobisisobutyronitrile were added and heated at 75 ° C. for 5 hours under a nitrogen stream to allow the polymerization reaction to proceed, and the copolymer solution (solid content). A concentration of 50 parts by mass) was obtained.
To this, 0.05 parts by mass of hydroquinone, 23 parts by mass of glycidyl methacrylate and 2.0 parts by mass of dimethylbenzylamine were added, an addition reaction was carried out at 80 ° C. for 24 hours, and then 35 parts by mass of carbitol acetate was added to solidify. A copolymer resin solution having an aromatic ring having a partial concentration of 50% by mass was obtained. Hereinafter, it is referred to as a carboxyl group-containing resin varnish D.

Example 1-1
<Preparation of photosensitive resin composition>
As a bifunctional or higher functional (meth) acrylate compound having a carboxyl group-containing resin varnish A obtained as described above, LMP-100 talc manufactured by Fuji Tarku Co., Ltd., and an isocyanul ring, ethoxylated isocyanuric acid triacrylate ( Shin-Nakamura Chemical Industry Co., Ltd., A9300), cresol novolac type epoxy resin (DIC Co., Ltd., N-695) and phenol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) as thermosetting epoxy resins. , RE-306), Omnirad 907 manufactured by IGM Resins, DETX-S manufactured by Nippon Kayaku Co., Ltd. and EAB manufactured by Daido Kasei Kogyo Co., Ltd. as a photopolymerization initiator, and crystalline silica (as other inorganic filler). Imcil A8) manufactured by Unimin Corporation, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) as a bifunctional or higher functional (meth) acrylate compound having no isocyanul ring, and DIC stock as a colorant. FASTOGEN GREEN S manufactured by the company, carbitol acetate and petroleum solvent (Solvesso 150 manufactured by Showa Kagaku Kogyo Co., Ltd.) as organic solvents are mixed in the proportions (parts by mass) shown in Table 1 below, and a stirrer is used. After premixing, the mixture was kneaded with a three-roll mill to prepare a photosensitive resin composition.

Examples 1-2-1-12 and Comparative Examples 1-1-1-3
A 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 as shown in Table 1.

The details of each component in Table 1 are as follows.
(1) Carboxylic group-containing resin, varnishes A to D (both blended amount as varnish)
(2) Tarku LMP-100 Tarku: manufactured by Fuji Tarku Co., Ltd. (3) Bifunctional or higher functional (meth) acrylate having an isocyanul ring, A9300: manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tri (meth) ethoxylated isocyanurate Aacrylate-A9300-CL: Caprolactone-modified ethoxylated isocyanuric acid tri (meth) acrylate-M-215: manufactured by Toa Synthetic Co., Ltd., ethoxylated isocyanurate di (meth) acrylate (4) epoxy resin N695: DIC Co., Ltd., cresol novolac type epoxy resin, RE-306: Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin, jER834: Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin, TEPIC-S: Nissan Triazine ring epoxy resin (5) Photopolymerization initiator, Omnirad 907: manufactured by IGM Resins, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, Omnirad, manufactured by Chemical Industry Co., Ltd. TPO: IGM Resins, 2,4,6-trimethylbenzoyldiphenylphosphine oxide / Kayacure DETX-S: Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone / EAB: Daido Kasei Kogyo Co., Ltd., 4, 4'-diethylaminobenzophenone (6) Other inorganic filler Imcil A8: manufactured by Unimin Corporation, crystalline silica Admafine SO-C5: manufactured by Admatex Co., Ltd., spherical silica A-26: manufactured by Sumitomo Chemical Co., Ltd. , Alumina B-30: Sakai Chemical Industry Co., Ltd., Barium sulfate (7) Bifunctional or higher (meth) acrylate / kayacure DPHA without isocyanul ring, Nippon Kayaku Co., Ltd., Dipentaerythritol hexa (meth) ) Acrylic M-350: Toa Synthetic Co., Ltd., ethoxylated trimetyl propanetri (meth) acrylate (8) Colorant, FASTOGEN GREEN S: DIC Co., Ltd. (9) Organic solvent, Solbesso 150: Showa Chemical Industry Co., Ltd. Made by company

Example 2-1
<Preparation of two-component photosensitive resin composition>
The carboxyl group-containing resin varnish A obtained as described above, LMP-100 talc manufactured by Fuji Tarku Co., Ltd., Omnirad 907 manufactured by IGM Resins Co., Ltd., DETX-S manufactured by Nippon Kayaku Co., Ltd., and the like as a photopolymerization initiator. EAB manufactured by Daido Kasei Kogyo Co., Ltd., crystalline silica (Imcil A8 manufactured by Unimin Corporation) as another inorganic filler, and dipentaerythritol as a bifunctional or higher functional (meth) acrylate compound having no isocyanul ring. Hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.), FASTOGEN GREEN S manufactured by DIC Corporation as a colorant, and carbitol acetate and petroleum solvent (Solvesso 150 manufactured by Showa Kagaku Kogyo Co., Ltd.) as organic solvents. , Are blended in the proportions (parts by mass) shown in Table 2 below, premixed with a stirrer, and kneaded with a three-roll mill to prepare the first composition.
As a bifunctional or higher functional (meth) acrylate compound having an isocyanul ring, ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A9300), and as an epoxy resin which is a thermosetting component, a cresol novolac type epoxy resin. (DIC Co., Ltd., N-695) and phenol novolac type epoxy resin (Nippon Kayaku Co., Ltd., RE-306), and carbitol acetate and petroleum solvent as organic solvents (Showa Chemical Industry Co., Ltd., Solvento 150) was blended in the proportions (parts by mass) shown in Table 2 below, premixed with a stirrer, and kneaded with a three-roll mill to prepare a second composition. A two-component photosensitive resin composition composed of a first composition and a second composition was obtained.
Then, the first composition and the second composition were mixed and stirred until uniform.

Examples 2-2-2-14 and Comparative Examples 2-1-2-3
A two-component photosensitive resin composition was prepared in the same manner as in Example 2-1 except that the compositions of the first composition and the second composition were changed as shown in Table 2. Then, the first composition and the second composition were mixed and stirred until uniform.

Example 3-1
<Preparation of photosensitive resin composition>
The carboxyl group-containing resin varnish A obtained as described above, synthetic mica MK-100 manufactured by Katakura Corp Agri Co., Ltd., and ethoxylated isocyanuric acid as a bifunctional or higher functional (meth) acrylate compound having an isocyanul ring. Triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A9300), cresol novolac type epoxy resin (manufactured by DIC Co., Ltd., N-695) as a thermosetting component epoxy resin, and IGM Resins as a photopolymerization initiator. Omnirad TPO manufactured by Nippon Kayaku Co., Ltd., DETX-S manufactured by Nippon Kayaku Co., Ltd., spherical silica (Admatex Co., Ltd., Admafine SO-C5) as other inorganic fillers, and bifunctional or higher functional without isocyanul ring. Table 1 below shows dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) as a (meth) acrylate compound, FASTOGEN GREEN S manufactured by DIC Co., Ltd. as a colorant, and carbitol acetate as an organic solvent. The epoxy resin composition was prepared by blending at the ratio shown in (1), premixing with a stirrer, and kneading with a three-roll mill.

Examples 3-2-3-7 and Comparative Examples 3-1-3-3
A 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 as shown in Table 3.

The details of each component in Table 3 are as follows. The description of duplicates in Table 1 will be omitted.
(2) Mica MK-100: Synthetic mica manufactured by Katakura Corp. Agri Co., Ltd., KAl ₂ (AlSi ₃ O ₁₀ ) F ₂ , average particle size 3.4 μm
-M-HF: Natural mica manufactured by Repco Co., Ltd., KAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ , average particle size 4 μm

Example 4-1
<Preparation of two-component photosensitive resin composition>
The carboxyl group-containing resin varnish A obtained as described above, MK-100 mica manufactured by Katakura Corp Agri Co., Ltd., Omnirad TPO manufactured by IGM Resins, and DETX-S manufactured by Nippon Kayaku Co., Ltd. as photopolymerization initiators. As other inorganic fillers, spherical silica (Admafine SO-C5 manufactured by Admatex Corporation) and dipentaerythritol hexaacrylate (Japan) as a bifunctional or higher functional (meth) acrylate compound having no isocyanul ring. DPHA) manufactured by Kayaku Co., Ltd., FASTOGEN GREEN S manufactured by DIC Corporation as a colorant, and carbitol acetate as an organic solvent are blended in the proportions (parts by mass) shown in Table 4 below, and put into a stirrer. After premixing, the mixture was kneaded with a three-roll mill to prepare a first composition.
As a bifunctional or higher functional (meth) acrylate compound having an isocyanul ring, ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A9300), and as an epoxy resin which is a thermosetting component, a cresol novolac type epoxy resin. (N-695 manufactured by DIC Co., Ltd.) and carbitol acetate as an organic solvent are mixed at the ratios (parts by mass) shown in Table 4 below, premixed with a stirrer, and then kneaded with a 3-roll mill. Then, the second composition was prepared. A two-component photosensitive resin composition composed of a first composition and a second composition was obtained.
Then, the first composition and the second composition were mixed and stirred until uniform.

<Preparation of evaluation board>
Each resin composition obtained by the above Examples and Comparative Examples (Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-3, Examples 4-1 to 4-9 and Comparative Example 4-1 For ~ 4-3, a mixture of the first resin composition and the second resin composition) was applied to the entire surface by screen printing on a circuit pattern substrate having a copper thickness of 35 μm, and dried at 80 ° C. for 30 minutes. , The mixture was allowed to cool to room temperature to form a resin layer having a thickness of 20 μm. The resin layer is subjected to solid exposure at the optimum exposure amount using an exposure device equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% sodium carbonate aqueous solution at 30 ° C. is developed at a spray pressure of 0.2 MPa for 60 seconds. went.
The substrate was irradiated with ultraviolet rays under the condition of an integrated exposure of 1000 mJ / cm ² in a UV conveyor furnace, and then heated at 160 ° C. for 60 minutes to cure the resin layer.

<Solder heat resistance>
The evaluation substrate produced as described above was coated with a rosin-based flux and then immersed twice in a solder bath at 260 ° C. for 30 seconds. Then, the appearance after washing the flux 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)
◯: No peeling of the cured resin layer was observed even after immersion in the solder bath.
Δ: When immersed in the solder bath, some peeling of the cured resin layer was observed.
X: Significant peeling of the cured resin layer was observed when immersed in the solder bath.

<Cold heat cycle resistance>
On the substrate on which the 2 mm copper line pattern was formed, each resin composition obtained in the above Examples and Comparative Examples was coated on the entire surface by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. An evaluation substrate on which 17 3 mm square resist patterns were formed was produced.
This evaluation substrate was placed in a thermal cycle machine in which a temperature cycle was performed between −65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. Then, the appearance after 1000 cycles was observed, the number of cracks was counted, and the evaluation was made based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4. The denominator value "68" is four corners (4) x 17 of a 3 mm square resist pattern, which means 68 corners, and the numerator value "30" or the like indicates the number of cracks. Represent.
(Evaluation criteria)
⊚: 20/68 or less ○: 21/68 or more and 30/68 or less Δ: 31/68 or more and 40/68 or less ×: 41/68 or more

<Prevention of deterioration of adhesion>
The evaluation substrate produced as described above was heated at 150 ° C. for 2000 hours using a hot air circulation type drying furnace DN610 manufactured by Yamato Scientific Co., Ltd. After that, the automatic cross-cut tester No. 1 manufactured by Coating Tester Co., Ltd. was applied to each evaluation board. Using 807-KS2, scratches were made so that there were 100 1 mm ² squares. After that, peeling of the resin layer was confirmed by tape peeling, and evaluation was made based on the following evaluation criteria. The evaluation results are summarized in Tables 1 to 4.
(Evaluation criteria)
◎: Peeling, no chipping 〇: Peeling, number of chips is 1 or more and 15 or less △: Peeling, number of chips is more than 15 and 35 or less ×: Number of peeling and chipping is more than 35 and 65 or less XX : More than 65 peeled and chipped

As is clear from the examples, it can be seen that the photosensitive resin composition of the present invention is remarkably excellent in all of heat resistance, adhesion deterioration prevention property, and cold cycle resistance.
Further, it can be seen that by making the photosensitive resin composition a two-component type, the adhesion deterioration prevention property and the thermal cycle resistance are further improved.

Claims (11)

Carboxylic acid-containing resin and
With at least one of talc and mica,
With a bifunctional or higher functional (meth) acrylate having an isocyanul ring,
Epoxy resin and
Only contains a light polymerization initiator,
A photosensitive resin composition comprising at least one of a novolak type carboxyl group-containing resin and a bisphenol type carboxyl group-containing resin as the carboxyl group-containing resin . The photosensitive resin composition according to claim 1 , which comprises at least one of a silicon oxide and aluminum oxide. The photosensitive resin composition according to claim 1 or 2 , which comprises a bifunctional or higher functional (meth) acrylate having no isocyanul ring. The photosensitive resin composition according to any one of claims 1 to 3 , which contains fluorine-containing mica as the mica. A two-component photosensitive resin composition comprising a first composition and a second composition.
The first composition comprises a carboxyl group-containing resin and a photopolymerization initiator.
The second composition comprises an epoxy resin and
At least one of the first composition and the second composition comprises at least one of talc and mica.
At least one of the first composition and the second composition has an isocyanuric ring, viewed contains a bifunctional or higher (meth) acrylate,
A two-component photosensitive resin composition, wherein the first composition contains at least one of a novolak type carboxyl group-containing resin and a bisphenol type carboxyl group-containing resin as the carboxyl group-containing resin . The two-component photosensitive resin composition according to claim 5 , wherein the first composition contains at least one of talc and mica. The two-component photosensitive resin composition according to claim 5 or 6 , wherein the second composition contains a bifunctional or higher functional (meth) acrylate having an isocyanul ring. The two-component photosensitive resin composition according to any one of claims 5 to 7 , wherein the first composition contains at least one of silicon oxide and aluminum oxide. The two-component photosensitive resin composition according to any one of claims 5 to 8 , wherein the first composition contains a bifunctional or higher functional (meth) acrylate having no isocyanul ring. The film and the photosensitive resin composition according to any one of claims 1 to 4 or the two-component photosensitive resin composition according to any one of claims 5 to 9 are applied to the film and dried. A dry film characterized by having a resin layer obtained from the above. The photosensitive resin composition according to any one of claims 1 to 4 , the two-component photosensitive resin original composition according to any one of claims 5 to 9 , or the dry film according to claim 10. A printed wiring board characterized by having a cured product obtained by curing the resin layer of.