JPS63280244A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To enable formation of a solder mask which can be developed by a fire retardant developing soln. and has excellent definition, heat resistance and surface gloss by using a specific photosensitive resin compsn. CONSTITUTION:This compsn. contains 100pts.wt. photopolymerizable unsatd. compd. obtd. by bringing isocyanate ethyl methacrylate into reaction with the secondary hydroxyl group of an unsatd. compd. obtd. by addition reaction of a specific novolak type epoxy resin and unsatd. carboxylic acid in a 0.1-0.98 range of acid equiv./epoxy equiv. ration in such a manner that an isocyanate equiv./hydroxyl group equiv. ratio attains a 0.1-1.2 range, 2-15pts.wt. 2- methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 20-100pts.wt. fine granular filler and 1-10pts.wt. heating hardener. The solder mask which can be developed by the fire retardant developing soln. and has the excellent definition, heat resistance and surface gloss is thereby formed.

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 manufacturing, metal precision processing, and the like.

(Prior Art) Photosensitive resin compositions having excellent properties that can be used as solder masks, resists for chemical plating, etc. are known in the printed wiring board industry.

The main purpose of a solder mask is to limit the area during soldering and prevent solder bridging, etc., to prevent corrosion of bare copper conductors, and to maintain electrical insulation between conductors over a long period of time. That's true.

By the way, solder masks are usually made of epoxy resin,
A mask whose main component is a thermosetting resin such as aminoplast resin (printed mask) is used.

However, in recent years, the wiring density of printed wiring boards has increased, and the requirements for electrical insulation between conductors have also become stricter, and the solder masks used for them are also required to be thick and have excellent dimensional accuracy. Printing methods are no longer able to cope with this problem.

Therefore, a photosensitive resin composition that forms a thick film (usually 25 μm on a conductor is desired) and a highly reliable solder mask with excellent dimensional accuracy using a photographic method (image formation by imagewise exposure followed by development). The appearance of things is desired.

Conventionally, as photosensitive resin compositions for forming solder masks, (1) photosensitive resin compositions containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-5'6018, JP-A-54 -1018, etc.), (2) A photosensitive resin composition containing as main components an epoxy resin imparted with photoreactivity and an epoxy resin curing agent (Japanese Patent Laid-Open No. 52-37996)
(3) Isocyanatoethyl methacrylate-modified photosensitive resin composition (Japanese Patent Application Laid-open No. 61-132947), etc. are known.

However, the photosensitive resin composition of (1) above is used in ordinary film photosensitive materials for etching and plating (for example, manufactured by DuPont, trade name Riston, manufactured by Hitachi Chemical Co., Ltd., trade name Photec, etc.). Flame retardant 1.1.
Although it can be developed with 1-trichloroethane and can form a high-resolution solder mask, such photosensitive resin compositions use a large amount of acrylic polymer to impart film properties, so the hardening of the cured film is difficult. It has the disadvantage of not having sufficient heat resistance.

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

Furthermore, the photosensitive resin composition of (3) above has a 1°1.1-
Can be developed with a developer such as trichloroethane, and has high resolution and
It also has excellent heat resistance, and when mixed with a filler mainly consisting of talc as disclosed in JP-A No. 58-62636, it improves the adhesion between the printed wiring board and the cured film, making it possible to create a highly reliable solder mask. However, the drawback is that the surface of the film lacks gloss due to damage during development. For this reason, there is a problem that scratches occur due to external factors before being used in final products such as electronic components, which impairs its value as a solder mask. (Objective of the Invention) In view of the above-mentioned problems, the present invention has been developed to provide a reliable and reliable product that can be developed with a flame-retardant developer such as 1.1.1-trichloroethane and has excellent resolution, heat resistance, and surface gloss. An object of the present invention is to provide a photosensitive resin composition that can form a high-quality solder mask.

(Means for Solving the Problems) The present invention provides one or more novolac-type epoxy resins selected from the group consisting of orthocresol novolac-type epoxy resins, phenol novolac-type epoxy resins, and halogenated phenol novolak-type epoxy resins. The resin and the unsaturated carboxylic acid have an acid equivalent/epoxy equivalent ratio of 0.
．． Isocyanate ethyl methacrylate is added to the secondary hydroxyl group of an unsaturated compound obtained by addition reaction in the range of 1 to 0.98, and the isocyanate equivalent/hydroxyl group equivalent ratio is 0°1 to 0.98.
(b) 2-15 parts by weight of 2-methyl-[4-(methylthio)phenyl-2-morpholino-1-propane, ( c) A photosensitive resin composition comprising 20 to 100 parts by weight of a particulate filler and (d) 1 to 10 parts by weight of a heat curing agent.

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

The novolak-type epoxy resin used in the present invention is obtained by reacting, for example, orthocresol, phenol, halogenated phenol, etc. with an aldehyde in the presence of an acid catalyst. It is obtained by reacting epichlorohydrin and is commercially available.

Orthocresol novolac type epoxy resins include:
For example, Araldite EcN129 manufactured by Ziba Geigy.
9 (softening point 99°C, epoxy equivalent 230>, ECN1
280 (softening point 80°C, epoxy equivalent 230>, EC
N1273 (softening point 73℃, epoxy weight @230)
, made by Nippon Herbal Medicine ■, EOCN104 (softening point 90-100
°C, epoxy equivalent 225-245), ECN123 (
Softening point 80-90°C, epoxy equivalent 215-235>,
ECN127 amount 215~235>, EOCNlol (softening point 65~
69°C, epoxy equivalent: 205 to 225).

As the phenol novolak type epoxy resin, for example, Epikote 154 (epoxy equivalent: 176 to
181), manufactured by Dow Chemical Company, DEN431 (epoxy equivalent: 172-179), DEN438 (epoxy equivalent: 175-1B2>, manufactured by Tobu Kasei ■, YDPN-638)
(Epoxy @ 170-190), YDPN-601 (
Epoxy equivalent: 180-220>, YDPN-602 (epoxy equivalent: 180-220), and the like.

Examples of the halogenated phenol novolac type epoxy resin include Nippon Herbal Pharmaceutical ■'74. Examples include brominated phenol novolak type epoxy resins such as BREN (epoxy equivalent: 270-300, bromine content: 35-37%, softening point: 80-90°C).

Further, as the unsaturated carboxylic acid, acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid, etc. are used.

In the present invention, the addition reaction between these novolak-type epoxy resins and unsaturated carboxylic acids is carried out by a conventional method at an acid equivalent/epoxy equivalent ratio of 0.1 to 0.9 as shown in formula (1).
This is done as a range of 8.

When the acid equivalent/epoxy equivalent ratio is less than 0.1, the photocured film is likely to swell during development treatment after image exposure. If the acid equivalent/epoxy equivalent ratio exceeds 0.98, adhesiveness, 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, cyclohexanone, etc., and a tertiary amine such as triethylamine, tri-n-butylamine, diethylcyclohexylamine, benzyltrimethyl chloride, etc. is used as a catalyst. Using a quaternary ammonium salt such as ammonium, benzyltriethylammonium chloride, etc., and hydroquinone, p-methoxyphenol, etc. as a polymerization inhibitor, the unsaturated carboxylic acid is stirred at 70 to 110°C in the equivalent ratio range mentioned above. By reacting, an unsaturated compound is obtained.

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

When the isocyanate equivalent/hydroxyl equivalent ratio is less than 0.1, development with a flame-retardant organic solvent such as 1,1,1-trichloroethane becomes difficult, and photocurability also decreases. When the isocyanate equivalent/hydroxyl group equivalent ratio exceeds 1.2, gelation tends to occur during the reaction, and properties such as heat resistance also deteriorate. After reaction, methanol, ethanol, 2
- It is desirable for safety and to improve storage stability to urethanize and deactivate the remaining isocyanatoethyl methacrylate using a primary alcohol such as hydroxyethyl methacrylate. As the isocyanate ethyl methacrylate, for example, one manufactured by Dow Chemical Company is used.

For example, an addition reaction is carried out between the above-mentioned novolac type epoxy resin and an unsaturated carboxylic acid, and then a urethanization catalyst such as dibutyltin dilaurate or dibutyldendi-2-ethylhexoate is added to the product to maintain the equivalent ratio within the above range. So, isocyanate ethyl methacrylate is 50 to 11
A photopolymerizable unsaturated compound is obtained by carrying out a stirring reaction at 0°C. Under such reaction conditions, side reactions such as the reaction between urethane bonds and epoxy groups and thermal polymerization of unsaturated bonds can be prevented, and as a result, photopolymerizable unsaturated compound can be obtained.

In the present invention, particularly preferred photopolymerizable unsaturated compounds include orthocresol novolac type epoxy resin/
Acrylic acid/isocyanatoethyl methacrylate-based reactant (acid equivalent/epoxy equivalent ratio 0.1-0.98, isocyanate equivalent/hydroxyl group equivalent ratio 0.1-1.2) Orthocresol novolac type epoxy resin/methacrylic acid/ Isocyanatoethyl methacrylate-based reactant (
Acid equivalent/epoxy equivalent ratio of 0.1 to 0.98, isocyanate equivalent/hydroxyl equivalent ratio of 0.1 to 1.2), and the like.

Next, the photosensitive resin composition of the present invention has 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane represented by the following formula (3) as an essential component (b), which is photopolymerized. Contains as an initiator.

Examples of 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane include IRGACURE 907 manufactured by Ciba Geigy.

The essential component (b) used in the present invention may be used alone, but may include substituted or unsubstituted polynuclear quinones, such as
2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2゜3-diphenylanthraquinone, etc.
Ketoaldonyl compounds such as diacetylbenzyl, benzoin.

α-ketoaldonyl alcohols and ethers such as pyrone, α-hydrocarbon-substituted aromatic acyloins, e.g.
-Phenyl-benzoin, α,α-jethoxyacetophenone, etc., benzophenone, aromatic ketones such as 4,4'-bisdialkylaminobenzophenone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2-
It may be used in combination with one or more thioxanthone sensitizers such as thioxanthone, 2-isopropylthioxanthone, and 2-ethylthioxanthone.

In addition, additives which do not have photoinitiating properties by themselves but which, when used in combination with the above substances, result in a sensitizer system with better photoinitiating performance as a whole, such as triethanolamine for benzophenone, etc. Tertiary amines, isoamyl dimethylaminobenzoate for thioxanthone, N-methyldietalamine, suethylaminobenzophenone, etc. can also be used.

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, hydrated silicic acid, aluminum hydroxide, alumina, barium sulfate, antimony trioxide, magnesium carbonate, mica powder, aluminum silicate, magnesium silicate, etc. are used. It will be done.

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

In addition, in order to increase the adhesive strength between the filler and the photopolymerizable unsaturated compound, the surface of the filler is coated with a silane coupling agent having a functional group such as a water group, an amine group, an epoxy group, or a vinyl group. It can also be processed with Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Can be mentioned.

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

Examples of heat curing agents include dicyandiamide, boron trifluoride monoethylamine combination, 2-methylimidazole, 2-heptadecyl imidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-
2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-
2-Undecyl imidazole trimellitate, 2.4-
Diamino-6-[2'-methyl-imidazole-(1)
”]-]ethyl-1.3.5-triazine2.4-diamino-6-[2”-ethyl-4'methylimidazolyl-
(1) 1-ethyl-1,3゜5-triazine, 2,4-
Diamino-6-[2”-undecyl imidazolyl (
1)'']-]ethyl-1.3.5-triazine latent curing agent is preferred.

In the photosensitive resin composition of the present invention, 2-methyl-
2 to 15 parts by weight of [4-(methylthio)phenyl]-2-morph t-lino-1-propane (b), a fine particulate filler (
20 to 100 parts by weight of c) and 1 part of heat curing agent (d)
It is used in a range of 10 parts by weight.

In the present invention, two or more of the components (a>(c) and (d)) may be used in combination. If the component (b) is less than 2 parts by weight, the photocurability will be poor, and if it exceeds 15 parts by weight, the surface Curing is too fast, making it difficult to harden the inside. If component (c) is less than 20 parts by weight, the residual strain during curing shrinkage is large and cracks and peeling are likely to occur. If it exceeds 100 parts by weight, the particles will be difficult to harden after development. The amount of component (cI) is set in the range of 1 to 10 parts by weight in view of the reactivity of the epoxy group, solvent resistance, and development residue.

Moreover, the photosensitive resin composition of the present invention may contain other photopolymerizable compounds.

Other photopolymerizable compounds include, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylhexamethylene diisocyanate/2-hydroxyethyl acrylate (1/2 molar ratio) reaction product, isocyanate ethyl methacrylate/water (
2/1 molar ratio) reactants, etc. Also, JP-A-5
Photopolymerizable compounds shown in JP 3-56018 can also be used. However, from the viewpoint of maintaining heat resistance, the content of these other photopolymerizable compounds is preferably 10% by weight or less based on the photopolymerizable unsaturated compound (a).

Furthermore, the photosensitive resin composition of the present invention may contain other subsidiary components. Secondary components include polymer binders,
Examples include thermal polymerization inhibitors, dyes, pigments, coatability improvers, antifoaming agents, flame retardants, and adhesion improvers.

The photosensitive resin composition of the present invention can be prepared by dip coating, 70-
A photosensitive layer having a thickness of 10 to 150 μm can be easily formed by directly coating the substrate to be processed and protected by a conventional method such as a coating method or a screen printing method. When coating, if necessary, the composition can be dissolved in a solvent. Examples of the solvent include methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, methyl cellosolve, methylene chloride, 1.1
．． Examples include 1-trichloroethane.

In addition, this solution is applied onto a film such as a polyethylene terephthalate film or a polyimide film by a knife coating method or a roll coating method, and the photosensitive element obtained by drying is laminated by heating and pressure on a substrate using a hot roll. It is also possible to form a photosensitive layer. At this time, the board is a printed wiring board etc. with conductor wiring lines formed on it.
In the case of having irregularities of m or more, it is preferable to laminate under a vacuum of 200 mm 1-1 g or less in order to prevent air from being entrained. As a device for this purpose, for example,
A laminating apparatus described in Japanese Patent No. 5-13341 is used. In addition, when using a support film that is opaque to actinic light, it is necessary to peel off the support film at the time of exposure.

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

Examples of the developer include 1, 1. A halogenated hydrocarbon such as 'l-trichloroethane is used.

It is also possible to use a cleaning agent containing 1,1,1-trichloroethane as a main component, such as Three-One EX (manufactured by Toagosei Chemical Co., Ltd.).

The image-like protective film obtained by the above method has properties as a corrosion-resistant film for ordinary etching, plating, etc., but after development, exposure to active light and heat treatment at 80 to 200°C are performed. By doing so, properties such as scratch resistance, adhesion, heat resistance, and solvent resistance can be improved, and a permanent protective film that satisfies the properties of a photosensitive resin composition such as a solder mask can be obtained.

(Example) Next, examples of the photosensitive resin composition according to the present invention will be described. "Parts" in the examples mean parts by weight.

Examples] (a) Synthesis A of photopolymerizable unsaturated compound, orthocresol novolac type epoxy resin, EO
CN-102 (Epoxy Tosei 230) 1095 parts Ethyl cellosolve acetate 800 parts B, acrylic acid 69 parts Benzyltrimethylammonium chloride 7 parts p-methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 163 parts Dibutyltin Dilaurate 0.5 parts Ethyl cellosolve acetate 100 parts, methanol
The above A was added to a 10-part reactor equipped with a thermometer, a stirrer, a cooling tube, and a dropper and capable of heating and cooling, and the temperature was raised to 60° C. while stirring to uniformly dissolve the mixture. B was added dropwise thereto over about 1 hour while maintaining the reaction temperature at 60°C. 80 over 2 hours after dropping B.
The temperature was raised to .degree. C. and stirred for about 15 hours under SO'C, and the acid value of the reaction system was brought 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, the reaction temperature was gradually raised to 80° C. over about 5 hours, then lowered to 60° C., D was added, and stirring was continued for about 1 hour. In this way, orthocresol novolac type epoxy resin with nonvolatile content of 57% by weight/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0)
2, isocyanate equivalent/hydroxyl group equivalent ratio=1.1) solution (1) of a photopolymerizable unsaturated compound was obtained.

(b) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (1) 1
75 parts (non-volatile content: 100 parts) of 2-methyl-[4-(methylthio)phenyl]-2-morph t-lino-1-propane (IRGACLJRE 907 manufactured by Ciba Geigy)
．． Same hereafter) 10 parts, Micro Ace p-4 (manufactured by Nippon Talc, ultrafine particle talc, average particle size 1.5 μm>7 parts, Crystallite 5V (manufactured by Ryumori, ultrafine particle silica, average particle size 5)
μm) 36 parts, phthalocyanine green 0.1 part, 2-
3 parts of methylimidazole and 0.1 part of Seven Dovelow (manufactured by Mitsubishi Monsando, polymethacrylate leveling material) were blended and mixed and dispersed using three rolls to prepare a solution of the photosensitive resin composition.

(c) Formation of a cured film The solution of the photosensitive resin composition obtained in (b) was coated on a copper-clad laminate (MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.), and the solution was applied for 20 minutes at room temperature. Dry for 20 minutes at ℃ to a thickness of 40℃.
A photosensitive layer of μm was formed.

The film was then exposed to light through a negative mask at 400 mJ/CIrt using a Phoenix 3000 type exposure machine manufactured by Oak Manufacturing Co., Ltd. After exposure, it was heated at 80°C for 5 minutes, left at room temperature for 30 minutes, and then treated with 1,1,1-trichloroethane.
Spray development was performed at 0° C. for 60 seconds. Next, Toshiba Electric Materials v/
After irradiating at 1 J/cm using a Toshiba ultraviolet irradiation device manufactured by J (rated voltage 200 V, rated consumption type cuff, 2 KW, compatible lamp H5600L/2, number of lamps 1),
A solder mask with excellent dimensional accuracy corresponding to a negative mask was obtained by heat treatment at 0° C. for 30 minutes. This solder mask has a glossy surface and excellent resistance to cold and thermal shock.
Solder the solder for 10 seconds with
After cleaning for 10 minutes at ℃, MIL-5TD-20
2E107D Condition B (-65℃ 30 minutes 1. Room temperature within 5 minutes, 125℃ 30 minutes) No cracking or peeling of the coating was observed in 50 cycles of thermal shock test, and the long-term reliability is very good. I found out that

Example 2 (a>Synthesis A of photopolymerizable unsaturated compounds, orthocresol novolak type epoxy resin, manufactured by Nippon Kayaku viJ, product name EOCN-104 (epoxy equivalent: 230> 920 parts, halogenated phenol novolak type epoxy resin 2 Nippon Kayaku) ■Made product name B
REN (epoxy equivalent 285>2
85 parts methyl cellosolve acetate 600 parts B,
Acrylic acid 288 parts Benzyltriethylammonium chloride 7 parts p-methoxyphenol 3 parts Methyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 620 parts Dibutyltin dilaurate 0.5 parts Methyl cellosolve acetate 100 parts
Using 10 parts of the above A-D, the other procedures were the same as in Example 1(a), and a non-volatile content of 54% by weight of oruncresol novolac type epoxy resin/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0.8, isocyanate equivalent/hydroxyl group equivalent ratio=1) A solution (2) of a photopolymerizable unsaturated compound was obtained.

(b) Preparation of photosensitive resin composition The solution of the photopolymerizable unsaturated compound obtained in (a) above (2
> 185 parts (non-volatile content: 100 parts), antimony trioxide (average particle size 0.15 μm > 3 parts, 2-methyl-[4-(
5 parts of methylthio)phenyl-2-morpholino-1-propane, 1 part of 2-methylthioxanthone, Hosmer M
(manufactured by Yushi Products Co., Ltd., phosphoric acid ester) and 0.1 part of an equimolar salt of benzotriazole, 0.02 parts of Victoria Guarable Blue, and 2 parts of 2-methylimidazole were mixed and dispersed using three rolls, and exposed to light. A solution of a synthetic resin composition was prepared.

Thereafter, a cured film 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 manufactured by Kyoto Kasei@ (epoxy equivalent: 180)
857 parts ethyl cellosolve acetate 600 parts B, cinnamic acid
176 parts acrylic acid 8
6 parts Benzyltrimethylammonium chloride salt 7 parts p-methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 369 parts Dibutyltin dilaurate 0.1 part Ethyl cellosolve acetate 100 parts Methanol
1. Using 10 parts A-D above. Otherwise, the same procedure as in Example 1(a) was carried out.
Acid equivalent/epoxy equivalent ratio = 0.5, isocyanate equivalent/hydroxyl equivalent ratio = 1) A solution of a photopolymerizable unsaturated compound (
3) was obtained.

(b) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (3) 1
54 parts (non-volatile content: 100 parts), Crystallite 210
1-41 (Tatsumori, γ-glycidoxypropyltrimethoxysilane-treated ultrafine silica, average particle size 1 μm) 5
0 parts, 2-methyl-[4-(methylthio)phenyl]-
10 parts of 2-morpholino-1-propane, 1 part of ethyl dimethylaminobenzoate, 0.1 part of phthalocyanine green
parts, 2 parts of dicyandiamide, 1 part of 2-methylimidazole
A solution of the photosensitive resin composition was prepared by mixing and dispersing 1 part and 5 parts of methyl cellosolve using a three-roll roll.

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

Comparative Example 1 The solution of the photopolymerizable unsaturated compound obtained in Example 1(a) (1
) 175 parts, 10 parts of benzophenone, Micro Ace p
-47 parts of Crystallite 5, 36 parts of Crystallite 5, 0.1 part of Phthalocyanine Green, 3 parts of 2-methylimidazole, and 0.1 part of Modaflow were blended and mixed and dispersed using three rolls. The cured film obtained in the same manner had excellent heat resistance, but did not have surface gloss.

Comparative Example 2 The solution of the photopolymerizable unsaturated compound obtained in Example 2(a) (2
) 175 parts, 3 parts of antimony trioxide, 5 parts of 2-methylthioxanthone, 1 part of isoamyl dimethylbenzoate, 0.1 part of an equimolar salt of Phosmer M and benzotrizole, 0.02 part of Victoria Pure Blue, 2 - A cured film obtained in the same manner as in Example 1(c) by blending 2 parts of methylimidazole and mixing and dispersing it with three rolls was obtained in Comparative Example 1.
It had excellent heat resistance as well, but did not have surface gloss.

Comparative Example 3 The solution of the photopolymerizable unsaturated compound obtained in Example 3(a) (3
), 154 parts of Crystallite 2101-41.50 parts, 7 parts of dimethylbenzyl ketal (manufactured by Ziba Geigy, trade name IRGACURE 651), 0.1 part of phthalocyanine green, 2 parts of dicyandiamide, 1 part of 2-methylimidazole, and methyl A cured film obtained by blending 5 parts of Cellosolve and mixing and dispersing it with a three-roll roll to produce 1q in the same manner as in Example 1(c) had excellent heat resistance, but did not have surface gloss.

(Effects of the Invention) The protective film obtained using the photosensitive resin composition of the present invention has excellent heat resistance and cold shock resistance, as is clear from the above Example 1 and Comparative Example 1. etching,
It can be used in combination with a corrosion-resistant film for plating, etc., and a permanent protective film such as a solder mask.

Furthermore, by using the photosensitive resin composition of the present invention,
1.1.1-Can be developed with a flame-retardant developer such as trichloroethane, can form a solder mask with excellent resolution, heat resistance, and surface gloss, and can form a thick film solder mask etc. by photographic method It is also possible.

Furthermore, the film formed using the photosensitive resin composition of the present invention has excellent chemical and physical properties, and therefore can be used as an interlayer insulating layer of multilayer printed wiring boards, photosensitive adhesives, paints, and plastic reliefs. It can also be used for printing plate materials, metal precision processing materials, etc.

Furthermore, this coating has the effect of sufficiently resisting organic solvents such as tricrene, methyl ethyl ketone, isopropyl alcohol, and toluene, and also resisting acidic or alkaline aqueous solutions.

Claims (1)

[Claims] (1) (a) One or more novolak epoxy resins selected from the group consisting of orthocresol novolac epoxy resins, phenol novolak epoxy resins, and halogenated phenol novolak epoxy resins and an unsaturated carboxylic acid. , isocyanate ethyl methacrylate is added to the secondary hydroxyl group of an unsaturated compound obtained by addition reaction with an acid equivalent/epoxy equivalent ratio in the range of 0.1 to 0.98.
．． (b) 2-methyl-[4-(methylthio)phenyl]-
A photosensitive resin composition comprising 2 to 15 parts by weight of 2-morpholino-1-propane, (c) 20 to 100 parts by weight of a particulate filler, and (d) 1 to 10 parts by weight of a heat curing agent.