JPH0814697B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION << Industrial Application Field >> The present invention relates to a photosensitive resin composition for forming a protective film used in printed wiring board production, precision metal processing, and the like.

<< Prior Art >> Conventionally, in the printed wiring board industry, a photosensitive resin composition having excellent properties, which can be used as a solder mask, a resist for chemical plating, etc., has been known.

The main purpose of the solder mask is to limit the soldering area during soldering, prevent solder bridges, etc., prevent corrosion of bare copper conductors, and maintain electrical insulation between conductors for a long period of time. is there.

By the way, as the solder mask, one having a thermosetting resin as a main component (printing mask) such as an epoxy resin or an aminoplast resin is usually used.

However, in recent years, the wiring density of printed wiring boards has increased, and the requirements for electrical insulation between conductors have become stricter, and the solder mask used for them has to be thick film and have excellent dimensional accuracy. The printing method cannot handle it.

Therefore, a photosensitive resin composition for forming a highly reliable solder mask having a thick film (usually desired to be 25 μm on the conductor) by a photographic method (an image is formed by development following imagewise exposure) and having excellent dimensional accuracy. The appearance of things is desired.

Conventionally, as a photosensitive resin composition for forming a solder mask, (1) a photosensitive resin composition containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-60518, JP-A-54-1018). (2) Photosensitive resin composition mainly composed of photoreactive epoxy resin and epoxy resin curing agent (JP-A-52)
-37996, JP-A-58-62636, etc.), (3) Isocyanatoethyl methacrylate-modified photosensitive resin composition (JP-A-61-132947), etc. are known.

However, the photosensitive resin composition of the above (1) is a film-shaped photosensitive material for ordinary etching and plating (eg DuPont, trade name: Liston, Hitachi Chemical Co., Ltd.).
Made of flame-retardant 1, used in the product name, Fotech, etc.
Although it can be developed with 1,1-trichloroethane and can form a high-resolution solder mask, such a photosensitive resin composition uses a large amount of an acrylic polymer for imparting film property, so that it is cured. There is a drawback that the heat resistance of the coating is not sufficient.

Further, the photosensitive resin composition of the above (2) is based on an epoxy resin and has excellent heat resistance of a cured film, but is insoluble in a flame-retardant organic solvent such as 1,1,1-trichloroethane. Therefore, it is necessary to use a flammable organic solvent such as cyclohexanone as the developing solution, which is disadvantageous in terms of safety.

Further, the photosensitive resin composition (3) can be developed with a developer such as 1,1,1-trichloroethane and has excellent resolution and heat resistance, and is disclosed in JP-A-58-62636. When a filler mainly composed of talc is mixed, the adhesiveness between the printed wiring board and the cured film is improved and a highly reliable solder mask is formed, but there is a drawback that the film surface is not glossy due to damage from development. . Therefore, there is a problem that scratches are generated by an external factor before it is used for a final product such as an electronic component, and the value as a solder mask is impaired.

<Object of the Invention> In view of the above problems, the present invention is capable of developing with a flame-retardant developer such as 1,1,1-trichloroethane, and a resolution,
An object of the present invention is to provide a photosensitive resin composition which is excellent in heat resistance and surface gloss and which can form a highly reliable solder mask.

<< Means for Solving Problems >> The present invention relates to one or more kinds of novolac type epoxy selected from the group consisting of orthocresol novolac type epoxy resin, phenol novolac type epoxy resin and halogenated phenol novolac type epoxy resin. Resin and unsaturated carboxylic acid, acid equivalent / epoxy equivalent ratio
Photopolymerizable unsaturated obtained by reacting the secondary hydroxyl group of the unsaturated compound obtained by addition reaction in the range of 0.1 to 0.98 with isocyanate ethyl methacrylate at an isocyanate equivalent / hydroxyl group equivalent ratio of 0.1 to 1.2. 100 parts by weight of compound, (b) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-12 15 to 15 parts by weight, (c) 20 to 100 parts by weight of finely divided filler, and d) A photosensitive resin composition containing 1 to 10 parts by weight of a heat curing agent.

The photosensitive resin composition according to the present invention has, as the essential component (a), one or more selected from the group consisting of orthocresol novolac type epoxy resin, phenol novolac type epoxy resin and halogenated phenol novolac type epoxy resin. Of the novolac type epoxy resin and the unsaturated carboxylic acid having an acid equivalent / epoxy equivalent ratio of 0.1
To 0.98, the photopolymerizable unsaturated compound obtained by reacting the secondary hydroxyl group of the unsaturated compound obtained by the addition reaction with isocyanate ethyl methacrylate at an isocyanate equivalent / hydroxyl group equivalent ratio of 0.1 to 1.2. Contains.

The novolak type epoxy resin used in the present invention is, for example, orthocresol, phenol, a halogenated phenol or the like and an aldehyde, a phenolic hydroxyl group of a novolac type resin obtained by reacting in the presence of an acid catalyst, in the presence of an alkali. , Is obtained by reacting epichlorohydrin, and is commercially available.

Examples of the orthocresol novolac type epoxy resin include Araldite ECN1299 manufactured by Ciba Geigy.
(Softening point 99 ° C, epoxy equivalent 230), ECN1280 (softening point 80
℃, epoxy equivalent 230), ECN1273 (softening point 73 ℃, epoxy equivalent 230), Nippon Kayaku Co., Ltd., EOCN104 (softening point 90-1
00 ℃, Epoxy equivalent 225-245), EOCN103 (Softening point 80-90
℃, epoxy equivalent 215-235), EOCN102 (softening point 70-80
℃, epoxy equivalent 215-235), EOCN101 (softening point 65-69
C., epoxy equivalent 205 to 225) and the like.

Examples of the phenol novolac type epoxy resin include Epicoat 154 (epoxy equivalent: 176 to 18 manufactured by Shell Co.).
1), made by Dow Chemical Co., DEN431 (epoxy equivalent 172--17)
9), DEN438 (epoxy equivalent 175-182), Tohto Kasei Co., Ltd.
Manufactured by YDPN-638 (epoxy equivalent 170-190), YDPN-601 (epoxy equivalent 180-220), YDPN-602 (epoxy equivalent 180-2)
20) etc.

Examples of the halogenated phenol novolac type epoxy resin include BREN (epoxy equivalent of 270, manufactured by Nippon Kayaku Co., Ltd.).
~ 300, bromine content 35 ~ 37%, softening point 80 ~ 90 ℃) brominated phenol novolac type epoxy resin and the like.

As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid and the like are used.

In the present invention, the addition reaction of these novolac type epoxy resin and unsaturated carboxylic acid can be carried out by a conventional method according to the formula (1)
As shown in, the acid equivalent / epoxy equivalent ratio is in the range of 0.1 to 0.98.

If the acid equivalent / epoxy equivalent ratio is less than 0.1, the photo-cured film is likely to swell due to the development treatment after image exposure. If the acid equivalent / epoxy equivalent ratio exceeds 0.98, the adhesion, heat resistance, etc. will decrease.

For example, the above novolac type epoxy resin is dissolved in an inert organic solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, and cyclohexanone, and a tertiary amine such as triethylamine, tri-n-butylamine, diethylcyclohexylamine, benzyl chloride is used as a catalyst. Using quaternary ammonium salts such as trimethylammonium and benzyltriethylammonium chloride, etc., and hydroquinone, p-methoxyphenol, etc. as a polymerization inhibitor, the unsaturated carboxylic acid at 70 to 110 ° C. within the above equivalent ratio range. The unsaturated compound is obtained by reacting with stirring.

As described above, the reaction of isocyanate ethyl methacrylate with the secondary hydroxyl group of the unsaturated compound obtained by the addition reaction of the novolac type epoxy resin with the unsaturated carboxylic acid is carried out by the conventional method as shown in the formula (2). The equivalent ratio / hydroxyl equivalent ratio is in the range of 0.1 to 1.2.

When the isocyanate equivalent / hydroxyl equivalent ratio is less than 0.1, it becomes difficult to develop with a flame-retardant organic solvent such as 1,1,1-trichloroethane, and the photocurability also deteriorates. If the isocyanate equivalent / hydroxyl equivalent ratio exceeds 1.2, gelation is likely to occur during the reaction, and heat resistance and other properties deteriorate. After the reaction, it is desirable from the viewpoint of safety and improvement of storage stability to urethaneize and deactivate the remaining isocyanate ethyl methacrylate using a primary alcohol such as methanol, ethanol or 2-hydroxyethyl methacrylate. As the isocyanate ethyl methacrylate, for example, one manufactured by Dow Chemical Co. is used.

For example, the addition reaction of the above-mentioned novolac type epoxy resin and unsaturated carboxylic acid is carried out, and then a urethanization catalyst such as dibutyltin dilaurate or dibutyltin di2-ethylhexoate is added to this product in the above equivalence ratio range. , Isocyanatoethyl methacrylate 50-110
A photopolymerizable unsaturated compound is obtained by stirring and reacting at 0 ° C. Under such reaction conditions, it is possible to prevent a side reaction such as a reaction between a urethane bond and an epoxy group and a thermal polymerization of an unsaturated bond, and as a result, a photopolymerizable unsaturated bond is formed without forming a gel-like substance. The compound can be obtained.

In the present invention, a particularly preferred photopolymerizable unsaturated compound is an orthocresol novolac type epoxy resin / acrylic acid / isocyanatoethyl methacrylate-based reaction product (acid equivalent / epoxy equivalent ratio 0.1 to 0.98, isocyanate equivalent / hydroxyl equivalent ratio). 0.1 to 1.2) Orthocresol novolac type epoxy resin / methacrylic acid / isocyanatoethyl methacrylate-based reaction product (acid equivalent / epoxy equivalent ratio 0.1 to 0.98, isocyanate equivalent / hydroxyl equivalent 0.1 to 1.2) and the like.

Next, the photosensitive resin composition according to the present invention has an essential component (b)
As 2-methyl-1- [4 represented by the following formula (3)
-(Methylthio) phenyl] -2-morpholinopropanone-1 Is contained as a photopolymerization initiator.

2-Methyl-1- [4- (methylthio) phenyl]-
Examples of 2-morpholinopropanone-1 include IRGACURE907 manufactured by Ciba-Geigy.

The essential component (b) used in the present invention may be used alone, but may be a substituted or unsubstituted polynuclear quinone, for example, 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.
Ketoandonyl compounds such as diacetylbenzyl, α-ketoaldonyl alcohols and ethers such as benzoin and pyrone, α-hydrocarbon-substituted aromatic acyloins such as α-phenyl-benzoin, α, α-diethoxyacetophenone, and benzophenone. , 4,4′-bisdialkylaminobenzophenone and other aromatic ketones, 2 methylthioxanthone, 2,4-diethylthioxanthone, 2
-It may be used in combination with one or more sensitizers of thioxanthones such as chlorothioxanthone, 2-isopropylthioxanthone and 2-ethylthioxanthone.

Further, although it has no photoinitiating property by itself, an additive which, when used in combination with the above substance, becomes a sensitizer system having better photoinitiating performance as a whole, such as triethanolamine for benzophenone. It is also possible to use a tertiary amine, isoamyl dimethylaminobenzoate for thioxanthones, N-methyldietal amine, bisethylaminobenzophenone and the like.

Next, the photosensitive resin composition of the present invention contains a fine particulate filler as an essential component (c).

As the particulate filler, for example, talc, silica, titanium oxide, clay, calcium carbonate, hydrous silicic acid, aluminum hydroxide, alumina, barium sulfate, antimony trioxide, magnesium carbonate, mica powder, aluminum silicate,
Magnesium silicate or the like is used.

The particle size of the fine particulate filler is preferably 0.01 to 10 μm, and more preferably 0.01 to 1.5 μm from the viewpoint of preventing the deterioration of the resolution and the adhesion of the cured film. The fine particulate filler is preferably uniformly dispersed in the photosensitive resin composition.

Further, in order to increase the adhesive force between the filler and the photopolymerizable unsaturated compound, the surface of the filler is a hydroxyl group, an amino group,
It can also be treated with a silane coupling agent having a functional group such as an epoxy group or a vinyl group. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like. Can be mentioned.

Further, the photosensitive resin composition of the present invention contains a heat curing agent as an essential component (d).

Examples of the heat curing agent include dicyandiamide, boron trifluoride monoethylamine Compux, 2-methylimidazole, 2-heptadecylimidazole, 1-
Benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-
Methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate, 2,4-
Diamino-6- [2'-methyl-imidazole-
(1) ′]-Ethyl-1,3,5-triazine, 2,4-diamino-6- [2′-ethyl-4′methylimidazolyl-
(1) ′]-Ethyl-1,3,5-triazine, 2,4-diamino-6- [2′-undecyl-imidazolyl-
Latent curing agents such as (1) ']-ethyl-1,3,5-triazine are preferred.

In the photosensitive resin composition according to the present invention, the amount of 2-methyl-based is 100 parts by weight of the photopolymerizable unsaturated compound (a).
2 to 15 parts by weight of 1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (b), 20 to 100 parts by weight of the fine particulate filler (c) and 1 of the heat curing agent (d). ~ 1
Used in the range of 0 parts by weight.

In the present invention, the components (a) (c) and (d) are 2
You may use together 1 or more types. If the amount of the component (b) is less than 2 parts by weight, the photocurability is poor, and if it exceeds 15 parts by weight, the surface is cured too quickly to harden the inside. If the amount of the component (c) is less than 20 parts by weight, residual strain during curing shrinkage is large and cracks and peeling are likely to occur, and if it exceeds 100 parts by weight, the particles are likely to be exposed on the surface after development, resulting in water resistance and gloss. Inferior. The component (d) is contained in the range of 1 to 10 parts by weight from the viewpoints of reactivity of epoxy group, solvent resistance, and residual development.

Further, the photosensitive resin composition according to the present invention may contain other photopolymerizable compound.

As other photopolymerizable compounds, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylhexamethylene diisocyanate / 2-hydroxyethyl acrylate (1/2 molar ratio)
Reactants, isocyanate ethyl methacrylate / water (2 /
(1 molar ratio) reaction products and the like. In addition, JP-A-53-560
It is also possible to use the photopolymerizable compound disclosed in JP-A-18. However, the content of these other photopolymerizable compounds is preferably 10% by weight or less with respect to the photopolymerizable unsaturated compound (a) in order to maintain heat resistance.

Further, the photosensitive resin composition of the present invention may contain other auxiliary components. Examples of secondary components include polymer binders, thermal polymerization inhibitors, dyes, pigments, coatability improvers, defoamers, flame retardants, and adhesion improvers.

The photosensitive resin composition of the present invention is directly coated on a substrate to be processed and protected by a conventional method such as a dip coating method, a flow coating method and a screen printing method to easily form a photosensitive layer having a thickness of 10 to 150 μm. be able to. If necessary, the composition can be dissolved in a solvent for coating. Examples of the solvent include methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, methyl cellosolve, methylene chloride, 1,1,1-
Trichloroethane etc. can be mentioned.

Further, this solution is applied onto a film such as a polyethylene terephthalate film or a polyimide film by a knife coating method, a roll coating method or the like, and a photosensitive element obtained by drying is heated and laminated on a substrate by using a heat roll. Then, the photosensitive layer can be formed. At this time, the substrate is 10 μm such as printed wiring board with conductor wiring line formed.
When it has irregularities of m or more, it is preferable to stack under a vacuum of 200 mmHg or less in order to prevent air entrapment. An apparatus for this purpose is, for example, Japanese Patent Publication No. 55-13341.
The laminating apparatus described in the publication is used. When a support film that is opaque to actinic light is used, it is necessary to peel off the support film during exposure.

Exposure and development of the photosensitive layer thus formed are carried out by a conventional method. That is, as a light source, an ultra-high pressure mercury lamp,
Using a high-pressure mercury lamp or the like, imagewise exposure is performed on the layer of the photosensitive resin composition directly or through a transparent film such as a polyethylene terephthalate film through a negative mask. After the exposure, if the transparent film remains, it is peeled off and developed.

As the developing solution, for example, a halogenated hydrocarbon such as 1,1,1-trichloroethane is used. Also, a cleaning agent containing 1,1,1-trichloroethane as a main component, such as Three One
EX (manufactured by Toagosei Kagaku Co., Ltd.) can also be used.

The image-wise protective film obtained by the above method has properties as a corrosion-resistant film for ordinary etching, plating, etc., but is exposed to active light and subjected to heat treatment at 80 to 200 ° C. after development. As a result, scratch resistance, adhesion, heat resistance,
Properties such as solvent resistance can be improved, and a permanent protective film satisfying the properties as a photosensitive resin composition such as a solder mask can be obtained.

<< Example >> Next, the Example is demonstrated about the photosensitive resin composition which concerns on this invention. "Parts" in the examples means parts by weight.

Example 1 (a) Synthesis of photopolymerizable unsaturated compound A. Orthocresol novolac type epoxy resin, EOCN-102 (epoxy equivalent 230) 1095 parts Ethyl cellosolve acetate 800 parts B. Acrylic acid 69 parts Benzyltrimethylammonium chloride 7 Part p-Methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C. Tosocyanate ethyl methacrylate 163 parts Dibutyltin dilaurate 0.5 part Ethyl cellosolve acetate 100 parts D. Methanol 10 parts Thermometer, stirrer, cooling tube and dropper attached The above A was added to a 5 liter reactor which can be heated and cooled, and the temperature was raised to 60 ° C. with stirring to uniformly dissolve it. While maintaining the reaction temperature at 60 ° C, B was added dropwise to this over about 1 hour. After the dropwise addition of B, the temperature was raised to 80 ° C. over 2 hours, and stirring was continued at 80 ° C. for about 15 hours to reduce the acid value of the reaction system to 1 or less.

Next, the temperature was lowered to 60 ° C, and C was uniformly added dropwise over about 3 hours while maintaining the reaction temperature at 60 ° C. After dropping C,
After gradually raising the reaction temperature to 80 ° C over about 5 hours,
The temperature was lowered to 60 ° C., D was added and stirring was continued for about 1 hour.
Thus, a solution of an orthocresol novolac type epoxy resin / acrylic acid / isocyanatoethyl methacrylate (acid equivalent / epoxy equivalent ratio = 0.2, isocyanate equivalent / hydroxyl equivalent = 1.1) -based photopolymerizable unsaturated compound having a nonvolatile content of 57% by weight (1) was obtained.

(B) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (1)
175 parts (nonvolatile content 100 parts) (IRGACU manufactured by Ciba-Geigy)
RE 907, same below) 10 parts, Microace p-4 (Nippon Talc, ultrafine particle talc, average particle size 1.5 μm) 7 parts, Crystallite 5V (Tatsumori, ultrafine particle silica, average particle size 5)
μm) 36 parts, phthalocyanine green 0.1 part, 2-methylimidazole 3 parts and modabro (manufactured by Mitsubishi Monsanto, polymethacrylate-based leveling material) 0.1 parts are mixed and dispersed by three rolls to prepare a photosensitive resin composition. The solution was adjusted.

(C) Formation of cured film The solution of the photosensitive resin composition obtained in (b) was applied onto a copper-clad laminate (MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.), and the mixture was kept at room temperature for 20 minutes and then at 80 minutes. It was dried at 0 ° C. for 20 minutes to form a photosensitive layer having a thickness of 40 μm. Next, through a negative mask, using a Phoenix 3000 type exposure machine manufactured by Oak Manufacturing Co., Ltd., 400 mJ / cm
Exposed at ² . After exposure, heat at 80 ℃ for 5 minutes, leave at room temperature for 30 minutes, and then use 1,1,1-trichloroethane at 20 ℃ for 6 minutes.
Spray developed for 0 seconds. Next, Toshiba Denshi Co., Ltd., Toshiba UV irradiation device (rated voltage 200V, rated power consumption 7.2K
W, compatible lamp H5600L / 2, number of lamps 1), 1
After irradiating with J / cm ² , heat treatment was performed at 150 ° C. for 30 minutes to obtain a solder mask excellent in dimensional accuracy corresponding to a negative mask.
This solder mask has surface gloss and excellent resistance to thermal shock, and has rosin flux A-226 (Tamura Kaken Co., Ltd.).
Manufactured by MIL-S, after soldering at 260 ° C for 10 seconds and further cleaning with trichlene at 25 ° C for 10 minutes.
TD-202E107D Condition B (-65 ℃ 30 minutes, normal temperature within 5 minutes, 12
In a thermal shock test of 50 cycles at 5 ° C for 30 minutes, cracking and peeling of the coating were not observed, and it was found that the long-term reliability was extremely excellent.

Example 2 (a) Synthesis of photopolymerizable unsaturated compound A. Orthocresol novolak type epoxy resin, Nippon Kayaku Co., Ltd. trade name EOCN-104 (epoxy equivalent 230) 920 parts halogenated phenol novolac type epoxy resin, Brand name BREN (epoxy equivalent 285) 285 parts Methyl cellosolve acetate 600 parts B. Acrylic acid 288 parts Benzyl triethylammonium chloride salt 7 parts p-Methoxyphenol 3 parts Methyl cellosolve acetate 100 parts C. Isocyanate Ethyl methacrylate 620 parts Dibutyltin dilaurate 0.5 part Methyl cellosolve acetate 100 parts D. Methanol 10 parts Orthocresol novolac type epoxy having a nonvolatile content of 54% by weight in the same manner as in Example 1 (a) except that the above A to D are used. Resin / acrylic acid / isocyanatoethyl methacrylate (acid equivalent / Epoxy equivalent ratio = 0.8, isocyanate equivalent ratio / hydroxyl equivalent ratio = 1) to obtain a solution (2) of photopolymerizable unsaturated compound.

(B) Preparation of Photosensitive Resin Composition To the solution (2) of the photopolymerizable unsaturated compound obtained in (a) above, 185 parts (nonvolatile content: 100 parts) of antimony trioxide (average particle size: 0.15 μm) 3 Part, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-15 (15 parts), 2-methylthioxanthone (1 part), Fosmer M (phosphoric acid ester, manufactured by Y Fat Products Co., Ltd.) and 0.1 parts equimolar salt of benzotriazole, Victoria Viewer Blue 0.02
And 2-methylimidazole (2 parts) were mixed and dispersed with a three-roll mill to prepare a solution of the photosensitive resin composition.

Then, a cured coating having surface gloss and excellent heat resistance was obtained in the same manner as in Example 1 (c).

Example 3 (a) Synthesis of photopolymerizable unsaturated compound A. Orthocresol novolac type epoxy resin, YDPN-638 (epoxy equivalent 180) manufactured by Tohto Kasei Co., Ltd. 857
Part Ethyl cellosolve acetate 600 parts B. Cinnamic acid 176 parts Acrylic acid 86 parts Benzyltrimethylammonium chloride 7 parts p-Methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C. Tosocyanate ethyl methacrylate 369 parts Dibutyltin dilaurate 0.1 parts Ethyl Cellosolve acetate 100 parts D. Methanol 10 parts Using the above-mentioned A to D, and otherwise the same as in Example 1 (a), orthocresol novolac type epoxy resin having a nonvolatile content of 65% by weight / cinnamic acid / acrylic acid / isocyanate. Natoethyl methacrylate (acid equivalent / epoxy equivalent ratio = 0.
5, a solution (3) of an isocyanate equivalent / hydroxyl equivalent = 1) type photopolymerizable unsaturated compound was obtained.

(B) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (3)
Crystallite 2101-41 in 154 parts (nonvolatile content 100 parts)
(Manufactured by Tatsumori, γ-glycidoxypropyltrimethoxysilane-treated ultrafine particle silica, average particle size 1 μm) 50 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 10 Parts, ethyl dimethylaminobenzoate 1 part, phthalocyanine green 0.1 part, dicyandiamide 2 parts, 2-methylimidazole 1 part and methyl cellosolve 5 parts were mixed and dispersed with a three-roll to prepare a solution of the photosensitive resin composition. .

Then, a cured coating having surface gloss and excellent heat resistance was obtained in the same manner as in Example 1 (c).

Comparative Example 1 In 175 parts of the solution (1) of the photopolymerizable unsaturated compound obtained in Example 1 (a), 10 parts of benzophenone and p-microace p were added.
-4 7 parts, crystallite 5V 36 parts, phthalocyanine green 0.1 part, 2-methylimidazole 3 parts, modaflow
A cured coating obtained by mixing 0.1 parts and mixing and dispersing with a three-roll mill in the same manner as in Example 1 (c) had excellent heat resistance, but did not have surface gloss.

Comparative Example 2 To 175 parts of the solution (2) of the photopolymerizable unsaturated compound obtained in Example 2 (a), 3 parts of antimony trioxide, 5 parts of 2-methylthioxanthone, 1 part of isoamyl dimethyl benzoate,
Example 1 was prepared by mixing 0.1 part of equimolar salt of phosmer M and benzotrizole, 0.02 part of Victoria-viewable and 2 parts of 2-methylimidazole, and mixing and dispersing with a three-roll mill.
The cured film obtained in the same manner as in (c) had excellent heat resistance as in Comparative Example 1, but did not have surface gloss.

Comparative Example 3 154 parts of the solution (3) of the photopolymerizable unsaturated compound obtained in Example 3 (a), crystallite 2101-41,50 parts, dimethylbenzyl ketal (manufactured by Ciba Geigy, trade name IRGACU
RE651) 7 parts, phthalocyanine green 0.1 part, dicyandiamide 2 parts, 2-methylimidazole 1 part and methyl cellosolve 5 parts were blended and mixed and dispersed with a three-roll to obtain in the same manner as in Example 1 (c). The cured coating is
Although it had excellent heat resistance, it did not have surface gloss.

<< Effects of the Invention >> The protective film obtained by using the photosensitive resin composition of the present invention is excellent in heat resistance and cold and thermal shock resistance as is clear from Example 1 and Comparative Example 1 above. It can be used as a corrosion-resistant film for etching, plating, etc., or as a permanent protective film for solder max.

Further, by using the photosensitive resin composition of the present invention, it is possible to develop with a flame-retardant developer such as 1,1,1-trichloroethane to form a solder mask excellent in resolution, heat resistance and surface gloss. In addition, it is possible to form a thick film solder mask or the like by a photographic method.

Furthermore, the coating film formed by using the photosensitive resin composition of the present invention has excellent chemical and physical properties, and therefore, the interlayer insulating layer of the multilayer printed wiring board, the photosensitive adhesive, the paint, the plastic relief. It can also be used as a printing plate material, a metal precision processing material, and the like.

Also, this coating is trichlene, methyl ethyl ketone,
It has the effect of sufficiently withstanding organic solvents such as isopropyl alcohol and toluene, and withstanding acidic aqueous solutions or alkaline aqueous solutions.

 ─────────────────────────────────────────────────── --- Continuation of front page (72) Inventor Noboru Sugazawa 4-13-1, Higashimachi, Hitachi, Ibaraki Prefecture, Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (56) Reference JP-A-61-264341 (JP, A) JP 61-199691 (JP, A) JP 61-132947 (JP, A) JP 62-10642 (JP, A)

Claims (1)

[Claims] 1. A compound of (a) one or more novolak epoxy resins selected from the group consisting of ortho-cresol novolak epoxy resins, phenol novolak epoxy resins and halogenated phenol novolak epoxy resins. Saturated carboxylic acid, acid equivalent / epoxy equivalent ratio in the range of 0.1 ~ 0.98 in the secondary hydroxyl group of the unsaturated compound obtained by addition reaction, isocyanatoethyl methacrylate isocyanato equivalent / hydroxyl equivalent ratio of 0.
100 parts by weight of a photopolymerizable unsaturated compound obtained by reaction in the range of 1 to 1.2, (b) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-12 15 to 15 parts by weight Parts, (c) 20 to 100 parts by weight of finely divided filler, and (d) 1 to 10 parts by weight of a heat curing agent.