JPS61264340A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To enable a solder mask capable of forming a thick film image high in resolution with an inflammable developing soln., superior in heat resistance and high in reliability to be formed by incorporating a photopolymerizable prepolymer obtained by reacting isocyanatoethyl methacrylate with the hydroxyl group of an unsatd. compd. obtained by additionally reacting unsatd. carboxylic acid with a compd. having an epoxy group. CONSTITUTION:The photopolymerizable prepolymer is obtained by reacting isocyanatoethyl methacrylate in an isocyanato equivalent/hydroxyl equivalent ratio of 0.1-1.2, with the hydroxyl group of an unsatd. compd. obtained by additionally reacting unsatd. carboxylic acid in an acid equivalent/epoxy equivalent ratio of 0.1-0.98, with a compd. having at least one epoxy group and optionally having a functional group except an epoxy group in the molecule. The photosensitive resin compsn. contains said prepolymer, a photopolymerizable monomer, and a sensitizer or its system to be allowed to produce a free radical by actinic rays.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition for forming a protective film that has excellent properties that can be used in printed wiring board production, metal precision processing, and the like.

(Prior Art) It is well known that a photosensitive resin composition is used to form a resist for plating or etching in the precision processing industry 2, for example, in the manufacture of printed wiring boards. Also recently, electroless plating masks.

Photosensitive resin compositions have also been used in the field of permanent masks such as solder masks.

The permanent mask is heat resistant, solvent resistant, and chemical resistant.

Electrical Properties 1 Since excellent properties such as mechanical properties are required, there are a limited number of photosensitive resins that can be used.

JP-A-52-117985 9% JP-A-54-101
No. 8, JP-A-53-56018, etc. disclose photosensitive resin compositions that can be used as permanent masks. However, these photosensitive resin compositions mainly contain a polymeric binder and a monomer and are not suitable for forming a thick protective film.

In other words, since these photosensitive resin compositions use a polymeric binder with a high glass transition temperature, when forming a photosensitive layer, the photosensitive resin composition is first mixed with toluene, methyl ethyl ketone, or methylene chloride. It is necessary to form a photosensitive layer by uniformly dissolving or dispersing it in an organic solvent such as, etc., applying it secondarily, and drying it. Therefore, when the film becomes thick,
υ where air bubbles are generated during drying, the resin tends to flow,
It is difficult to form a uniform protective film.

Special Publication No. 55-127097, 4! Kaisho 49-10
Publication No. 7048 proposes a solvent-free photosensitive resin composition that can be used as a permanent mask. However, these liquid compositions are unsuitable for forming thick films and high-resolution protective films. Namely.

These liquid compositions use epoxy acrylate, which has poor solubility, resulting in poor developability.

Film photosensitive materials for ordinary etching and plating (
It is difficult to form thick films and high-resolution images with flame-retardant developers such as 1,1,1-trichloroethane, which are used in DuPont's Riston, Hitachi Chemical's Fotec, etc.), and the sensitivity is also low. It is not necessarily sufficient.

(Problem that the invention attempts to solve) The object of the present invention is to eliminate the drawbacks of the prior art.

1.1.1- A photosensitive resin composition capable of forming a thick film, high-resolution image with a flame-retardant developer such as trichloroethane, and a highly reliable solder mask with excellent heat resistance. It is about providing.

(Means for solving problems) The present invention is.

(a) A compound having at least one epoxy group and an unsaturated carboxylic acid are combined in an acid equivalent/epoxy equivalent ratio of 0.
．． Inocyanate ethyl methacrylate is added to the unsaturated compound obtained by addition reaction in the range of 1 to 0.98 to the hydroxyl group of the unsaturated compound, and the incyanate equivalent/hydroxyl group equivalent ratio is in the range of 0.1 to 1.2. A photopolymerizable prepolymer obtained by reacting with (b) a photopolymerizable monomer, and (e) a photosensitive resin containing a sensitizer and/or a sensitizer system that generates free radicals by actinic light. Regarding the composition.

The photosensitive resin composition of the present invention has as an essential component a).

A compound having at least one epoxy group and an unsaturated carboxylic acid are mixed at an acid equivalent/epoxy foil amount ratio of 0.1 to 0.
To the unsaturated compound obtained by addition reaction in the range of 98,
It contains a photopolymerizable prepolymer obtained by reacting incyanato ethyl methacrylate with the hydroxyl groups of an unsaturated compound at an incyanato equivalent/hydroxyl group equivalent ratio of 0.1 to 1.2.

A compound having at least one epoxy group.

In addition to the epoxy group, there are functional groups other than the epoxy group 9 in the molecule, such as hydroxyl, acrylic, and methacrylic groups.

It can have an acrylic group, etc.

As a compound having at least one epoxy group, 2
For example, bisphenol A type epoxy resin obtained by reacting bisphenol A and epichlorohydrin (e.g., Shell Chemical Epikote 8121, Epikote 828)
．． Epikote 1001, etc.) Brominated bisphenol A type epoxy resin (e.g. Ebitoto YDB-3 manufactured by Tobu Kasei ■)
40, YDB-400, etc.), bisphenol F type epoxy resin (e.g. Evototo YDF-170 manufactured by Tobu Kasei ■)
゜YDF-190, etc.), epoxy compounds obtained by adding bisphenol AK alkylene oxide and reacting with Evita Ruhydrin (e.g., Evolite 3002, manufactured by Kyoeisha Yushi), hydrogenated bisphenol A type epoxy resins (e.g., manufactured by Tobu Kasei). Suntote 5T-1000
, 5T-3000, etc.).

Glyoxal type epoxy resin (e.g. Evototo YDG-414 manufactured by Tobu Kasei), glycidylamine type epoxy resin (e.g. Evototo YDM-12 manufactured by Tobu Kasei ■)
0, YH-434, etc.), orthocresol novolac type epoxy resin (e.g. EOCNI O2 manufactured by Nippon Kayaku ■), phenol novolac type epoxy resin (e.g. YDPN-6388 manufactured by Tobu Kasei ■), brominated phenol novolac type epoxy resin ( For example, BREN manufactured by Nippon Kayaku ■
etc).

Alicyclic epoxy compounds (e.g., Chissonox 221, Chissonox 201, manufactured by Chisso ■), glycidyl ether type epoxy resins obtained by the reaction of dicarboxylic acids such as heptalic acid with epichlorohydrin (for example, Shodine, manufactured by Showa Denko ■) 508°Shodine 540.Shodine 550, etc.).

Examples include epoxidized polybutadiene, glycidylamine type epoxy resin (Epicote 604 manufactured by Shell Chemical Company, etc.), trimethylalpropane polyglycidyl ether, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and the like.

Unsaturated carboxylic acids include acrylic acid, methacrylic acid,
β-furyl acrylic acid, β-steryl acrylic acid, α-
Cyanocinnamic acid, cinnamic acid, etc. are used.

In the present invention, the addition reaction between a compound having at least one epoxy group and an unsaturated carboxylic acid is expressed by the formula (
As shown in I), the acid equivalent/epoxy equivalent ratio is 0.
It is carried out in a conventional manner within the range of 1 to 0.98. Acid equivalent/
If the epoxy equivalent ratio is less than 0.1, the photocured coating is likely to swell during development treatment after image exposure. If the acid equivalent/epoxy equivalent ratio exceeds 0.98, adhesion, heat resistance, etc. will decrease.

...(1) The unsaturated compound of the present invention is 9 For example, a tertiary amine such as triethylamine, tri-n-butylamine, diethylcyclohexylamine, etc., a quaternary ammonium salt such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, etc. as a catalyst, In addition, hydroquinone, p-methoxyphenol, etc. are used as polymerization inhibitors, and 70 to 11
It can be obtained by stirring and reacting the unsaturated carboxylic acid with the epoxy group-containing compound at 0°C. In this reaction, organic solvents such as methyl ethyl keto/, methyl cellosolve acetate, and 1,1.1-trichloroethane, and photopolymerizable monomers such as polypropylene glycol diacrylate and ethyl calpitol acrylate can be used as reaction solvents. .

The reaction of incyanatoethyl methacrylate to an unsaturated compound obtained by addition reaction of a compound having an epoxy group and an unsaturated carboxylic acid as described above is expressed by the formula (n).
The reaction of inocyanate ethyl methacrylate to all the hydroxyl groups of the unsaturated compound is carried out by a conventional method at an inocyanate equivalent/hydroxyl group equivalent ratio of 0.1 to 1.2. When the hydroxyl group equivalent ratio is less than 0.1, development with a flame-retardant organic solvent such as $11111-trichloroethane becomes difficult, and photocurability also decreases. When the incyanate equivalent/hydroxyl group equivalent ratio exceeds 1.2, gelation tends to occur during the two reactions;
In addition, properties such as heat resistance are also reduced. After reaction.

From the viewpoint of safety and improving storage stability, it is desirable to urethane and deactivate the remaining incyanatoethyl methacrylate using an alcohol such as methanol, ethanol, or 2-hydroxyethyl acrylate.

As isocyanate ethyl methacrylate.

For example, those manufactured by Dow Chemical Company are used.

" H For example, an addition reaction is carried out between the above-mentioned compound having at least one epoxy group and an unsaturated carboxylic acid, and then a urethanization catalyst such as dibutyltin dilaurate or dibutyltin di-2-ethyl hekynate is added to the product. A photopolymerizable prepolymer can be obtained by stirring and reacting isocyanatoethyl methacrylate at 50 to 110°C in the above equivalent ratio range.Under such reaction conditions, the reaction between urethane bonds and epoxy groups, unsaturation Side reactions such as thermal polymerization of bonds can be prevented, and as a result, a photopolymerizable prepolymer can be obtained without forming a gel-like substance.

Particularly preferred photopolymerizable prevolmers in the present invention include orthocresol novolac type epoxy resin/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio 0.1 to 0.98, isocyanate equivalent/hydroxyl group equivalent ratio 0.98). 1-1.2) System reactant, orncresol novolac type epoxy resin/methacrylic acid/
Incyanate ethyl methacrylate (acid equivalent/epoxy equivalent ratio 0.1-0.98, incyanato equivalent/hydroxyl equivalent ratio 0.1-1.2) unreacted material, bisphenol A
Type epoxy resin/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio 0.1-0.9
8. Isocyanate equivalent/hydroxyl equivalent ratio 0.1 to 1.2
) system reactant, bisphenol A type epoxy resin/methacrylic acid/isocyanatoethyl methacrylate (
Acid equivalent/epoxy equivalent ratio 0.1-0.98.

Incyanate equivalent/hydroxyl group equivalent ratio of 0.1 to 1.2) type reactants, etc. may be mentioned.

The photosensitive resin composition of the present invention contains a photopolymerizable monomer as an essential component (b). As this photopolymerizable monomer, known ones are used.

Preferred photopolymerizable monomers include butoxyethyl acrylate, ethylcarpitol acrylate, methyl triglycol acrylate, tetrahydrofurfuryl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate.

Monofunctional monomers such as phenoxyethyl methacrylate and cyclohexyl acrylate, trimethylolfuropane, trimethylolethane, pentaerythritol, cichentaerythritol, 1,3-butylene glycol, 1
．． 4-Butylene glycol.

1.5-pentadiol, polycaprolactone diol, polyglobylene glycol, decamethylene glycol, glycerin, neopentyl glycol, 2.2-bis(4,4' (2-hydroxyethoxy)phenyl)propane, tris(2- Esters of polyhydric alcohols such as hydroxyethyl isocyanuric acid and acrylic acid or methacrylic acid, phthalic anhydride-diethylene glycol-acrylic acid (1/2/2 molar ratio) wire mesh, trimethylolpropane-tetrahydrophthalic anhydride Acid - Acrylic acid (
Examples include low-molecular polyester resins having an acryloyloxy group and/or methacryloyloxy group at the end of a condensate (mole ratio of 2/1/4).

A reaction product of diol monoacrylate or diol monomethacrylate and diisocyanate, a reaction product of inocyanatoethyl methacrylate/water (2/1 molar ratio), etc., as described in Japanese Patent Publication No. 52-43092, etc., can also be used.

The photosensitive resin composition of the present invention contains, as an essential component (c), a sensitizer that generates free radicals by actinic light and a sensitizer system.

As the sensitizer, substituted or unsubstituted polynuclear quinones 9 such as 2-ethylanthraquinone, 2-1-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc. Ketoaldonyl compounds such as diacetylbenzyl,
α-ketaldonyl alcohols and ethers such as benzoin and pivalone, and α-hydrocarbon-substituted aromatic acyloins.

For example, aromatic ketones such as α-phenyl-benzoin, α, α-jethoxyacetophenone, benzophenone, 4,4′-bisdialkylaminobenzophenone,
2-methylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone.

Thioxanthone such as 2-isopropylthioxanthone and 2-ethylthioxanthone are used.

These may be used alone or in combination.

As a sensitizer system, for example, a combination of 2.4.5-IJ allylimidazole dimer and 2-mercaptobenzoquinazole, leuco crystal violet, tris(4-diethylamino-2-methylphenyl)methane, etc. used. In addition, additives such as triethanolamine for benzophenone, etc., which do not have photoinitiating properties by themselves, but when used in combination with the above-mentioned substances, provide a sensitizer system with better photoinitiating performance as a whole. isoamyl dimethylaminobenzoate, N-methyldietheramine,
Bisethylaminobenzophenone and the like can also be used.

The photosensitive resin composition of the present invention comprises (a) 100 parts by weight of the above photopolymerizable prepolymer, (b) 1 to 400 parts by weight of the above photopolymerizable monomer, and (c) the above increaser. It is preferable to use the sensitizer and/or sensitizer system in an amount of 0.1 to 30 parts by weight in order to form a solder mask with excellent resolution and soldering heat resistance.

Furthermore, the photosensitive resin composition of the present invention may contain other subsidiary components. As a secondary ingredient.

Thermal polymerization inhibitors, dyes, pigments, polymer binders, fillers,
Coatability improver, antifoaming agent, flame retardant, flame retardant aid.

Examples include adhesion improvers and latent curing agents for epoxy resins.

The photosensitive resin composition of the present invention is prepared using a roll coating method.

A photosensitive layer having a thickness of 10 to 200 μm can be easily formed on a substrate to be processed and protected by a conventional method such as a screen printing method or a flow coating method.

Further, the formation of the photosensitive layer is described in Japanese Patent Publication No. 48-23284,
This can be carried out using a conventional coating apparatus for liquid type photosensitive resins, such as those disclosed in Japanese Patent Laid-Open Nos. 49-43701 and 46-39404.

Exposure and development of the photosensitive layer thus formed are carried out by conventional methods. That is, an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, or the like is used as a light source, and imagewise exposure is performed through a negative mask. Polyethylene terephthalate film between the negative mask and the photosensitive resin layer to prevent the resin from adhering to the negative mask.

It is also possible to interpose a transparent cover film such as a polypropylene film, cellulose acetate film, or polycarbonate film. As the cover film becomes thicker, the resolution tends to decrease, so the thickness should be 25mm.
It is desirable that the thickness be less than μm.

It is also possible to expose the negative mask at a distance of about 0.3 mm from the photosensitive layer. After exposure, if a cover film remains, peel it off and then develop.

The type of developer used in the development process is not particularly limited as long as it does not damage the exposed areas and selectively elutes the unexposed areas. As a developer, 9, for example, 1
．． 1.1- Logonized hydrocarbons such as trichloroethane are used. It is also possible to use a cleaning agent 1 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 it must be exposed to active light and heat treated at 80 to 200°C. By carrying out this process, the properties can be further improved and a permanent protective film satisfying the properties as a solder mask can be obtained.

The order of exposure to active light and heat treatment may be in any order.

(Effects of the Invention) The protective film obtained using the photosensitive resin composition of the present invention has sufficient resistance to 14 solvents such as tricrene, methyl ethyl ketone, isopropyl alcohol, and toluene, and is also resistant to acidic or alkaline aqueous solutions. Furthermore, since it has excellent heat resistance and mechanical properties, it can be used as a corrosion-resistant film for etching, plating, etc., and as a permanent protective film for solder masks, etc. 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 a multilayer printed wiring board.

It can also be used in photosensitive adhesives, paints, plastic reliefs, printing plate materials, metal precision processing materials, etc.

Furthermore, by using the photosensitive resin composition of the present invention, 9
, 1,1.1-trichloroethane or the like, and a solder mask with excellent resolution and heat resistance can be formed. Furthermore, it is possible to form a thick film solder mask using a photographic method.

(Example) Parts in the examples mean parts by weight.

Example 1 (a) Synthesis of photopolymerizable prepolymer Bisphenol A epoxy resin, Epicoat 82
8 (Epoxy equivalent weight 190) 380 parts tripropylene glycol diacrylate 140 parts B, acrylic acid 93.6 parts Be/Dyltrimethylammonium chloride 0.4 parts p-methoxyphenol 0.6 parts C0 incyanatoethyl methacrylate 214 parts Dibutyl Chinjilaurate 0.1 part, methanol
Heating and cooling possible 11 with 5-part thermometer, stirrer, cooling tube and dropper! The above A was added to the reactor, and the temperature was raised to 100° C. while stirring to uniformly dissolve. While keeping the reaction temperature at 100°C.

B was added dropwise to this over about 30 minutes. After dropping B.

After stirring at 100° C. for about 20 hours, 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 second reaction temperature at 60°C. After C was added dropwise, the reaction temperature was gradually raised to 80° C. over about 5 hours, and then the temperature was lowered to 60° C., D was added, and stirring was continued for about 1 hour. In this way, bisphenol A type epoxy resin/
A mixture (I) containing 82% by weight of an acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0.65, incyanato equivalent/hydroxyl group equivalent ratio = 1.06) based photopolymerizable prepolymer was obtained.

(b) Preparation of photosensitive resin composition (photopolymerizable prepolymer-containing mixture (11
120 parts (99.6 parts of photopolymerizable prepolymer, photopolymerizable monomer, tripropylene glycol diacrylate) 20
．． A photosensitive resin composition of the present invention was prepared by mixing 1 part, 0.3 parts of others), 4 parts of diethylthiochibuntone, 5 parts of isobutyl dimethylaminobenzoate, and 0.01 part of Victoria Pure Blue.

(c1 Formation of a cured film The photosensitive resin composition obtained in step (b) was coated on a copper-clad laminate to form a photosensitive layer with a thickness of 80 μm.

The film was then exposed to light at 500 mJ/C- through a negative mask using a Phoenix 3000 type exposure machine manufactured by Oak Manufacturing Co., Ltd. The negative mask was placed 0.1 m away from the photosensitive layer, and the exposure was performed in the atmosphere. After exposure, it was heated at 80°C for 5 minutes and left at room temperature for 30 minutes.

90 at 20'C using 1,1,1-trichloroethane
Spray developed for seconds. Next, a Toshiba ultraviolet irradiation device manufactured by Toshiba Denzai ■ (rated voltage 200V, rated power consumption cuff, 2 tubes, compatible lamp H5600L/2. Number of lamps: 1)
After irradiating with IJ/cm" using
A solder mask with excellent dimensional accuracy corresponding to a negative mask was obtained by heat treatment for a minute. This solder mask has excellent cold and thermal shock resistance, and is soldered using rosin-based flux A-226 (Tamura Kaken ■!Ii!) at 260℃ for 10 seconds, and then cleaned with Triclean for 10 minutes at 25℃. After processing, MIL-8TD-202E 107D
Condition B (-65℃ 30 minutes, room temperature within 5 minutes, 125℃3
0 minutes).

No cracking or peeling of the coating was observed in the 50-cycle thermal shock test, indicating that the product has excellent long-term reliability.

Example 2 122 parts of the photopolymerizable prepolymer-containing mixture (1) obtained in Example 1(a) (100 parts of photopolymerizable prepolymer).

22 parts of tripropylene glycol diacrylate).

7 Talic anhydride/diethylene glycol/acrylic acid (1
/2/2 molar ratio) 30 parts of wire mesh, Kumgon Japanese talc■
30 parts of ultrafine particles manufactured by Merck, 4 parts of 1-(0)lyl) biguanide and 0.1 part of phthalocyanine green were kneaded using three rolls.

A photosensitive resin composition of the present invention was prepared.

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

Example 3 (a) Synthesis of photopolymerizable prepolymer A, orthocresol novolac type epoxy resin, EC
N1235 (manufactured by Ciba Geigy).

Epoxy equivalent weight 230) 460 parts ethylcarpitol acrylate) 140 parts Part B. lylic acid
36 parts benzyltriethylammonium chloride o, i parts p-methoxyphenol
0.6 parts C3 incyanato ethyl methacrylate 77.5 parts dibutyltin dilaurate
Orthocresol novolac type epoxy resin/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0 .25. Incyanate equivalent/hydroxyl group equivalent ratio=1) A mixture (If) containing 80% by weight of a photopolymerizable prepolymer was obtained.

(b) Preparation of photosensitive resin composition (photopolymerizable prepolymer obtained in al/photopolymerizable monomer mixture (11125 parts (100 parts photopolymerizable prepolymer,
25 parts of ethylcarpitol acrylate).

Trimethylhexamethylene diinocyanate/2-hydroxyethyl acrylate (1 part 2 molar ratio) Reactant 10
0 parts, antimony trioxide 6 parts, λ4-diethylthioxanthone 4 parts, dimethylamine ethyl benzoate 4 parts, equimolar salt of Phosma M (sulfuric acid ester produced by oil and fat products ■) and benzotriazole 0, 1 part, and Victoria A photosensitive resin composition of the present invention was prepared by kneading 0.02 part of Pure Blue using three rolls.

Thereafter, a crushable coating with excellent heat resistance was obtained in the same manner as in Example 1(c).

Further, the photosensitive resin composition had a thickness of 0.8 mm and a UL94
V-0 glass epoxy flame retardant base material (M made by Hitachi Chemical Co., Ltd.)
It was found that when applied to both sides of CL-E-67) to form a cured film with a thickness of 75 μm, flame retardancy of UL94V-1 was maintained.

Example 4 (a) Synthesis A of photopolymerizable prepolymer, bisphenol A type epoxy resin, Epicoat 82
8 (Epoxy equivalent: 1901 380 parts B, methacrylic acid 86 parts Benzyltrimethylammonium chloride 0.3 parts p-methoxyphenol
0.6 parts C0 incyanato ethyl methacrylate 31 parts dibutyltin dilaurate
Bisphenol A type epoxy resin/methacrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio=
0.5, Incyanate equivalent/hydroxyl group equivalent ratio=0.
2) A mixture (ml) containing photopolymerizable prepolymer was obtained.

(b) Preparation of photosensitive resin composition Mixture 10 containing the photopolymerizable prepolymer obtained in (a)
0L) Dimethylhexamethylene diinocyanate/2-
200 parts of hydroxyethyl acrylate (l/2 molar ratio) reactant, 15 parts of 2-hydroxyethyl methacrylate, 60 parts of Simbon (ultrafine talc manufactured by Nippon Talc ■),
4 parts of 44-diethylthioxanthone, 5 parts of isobutyl dimethylaminobenzoate, and Curazol 2E4MZ-
Two parts of A (imidazole curing agent manufactured by Shikoku Fine Chemicals ■) were blended and mixed using three rolls to prepare nine photosensitive resin compositions of the present invention.

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

Example 5 (a) Synthesis A of photopolymerizable prepolymer, bisphenol A type epoxy resin, Epicoat 10
01 (Epoxy equivalent: 470. Hydroxyl equivalent: 350)
235 parts tripropylene glycol diacrylate 150 parts B, acrylic acid 30 parts Benzyltrimethylammonium chloride 0.6 parts p-methoxyphenol 0.8 parts C, incyanatoethyl methacrylate 168 parts Dibutyltin dilaurate 0.1 parts Methanol
Bisphenol A type epoxy resin/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0.62. isocyanate equivalent/water A mixture (IV) containing 73 units of a photopolymerizable prepolymer (Shun group equivalent ratio=1) was obtained.

(b) 1137 parts of the photopolymerizable prepolymer/photopolymerizable monomer mixture flV obtained in step (1) (100 parts of photopolymerizable prepolymer,
37 parts of ethylcarpitol acrylate).

Trimethylhexamethylene diisocyanate/2-hydroxyethyl acrylate (1 part 2 molar ratio) Reactant 10
0 parts of Shimbot, 60 parts of 2,4-diethylthioxanthone, 5 parts of isobutyl dimethylaminobenzoate, and 2 parts of Curazole C1l Z AZINE (manufactured by Shikoku Fine Chemicals, imidazole-based curing agent) were kneaded using three rolls. 1. A photosensitive resin composition of the present invention was prepared.

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

Claims (1)

[Claims] 1. (a) A compound having at least one epoxy group and an unsaturated carboxylic acid are combined in an acid equivalent/epoxy equivalent ratio of 0.
．． To the unsaturated compound obtained by addition reaction in the range of 1 to 0.98, isocyanate ethyl methacrylate is added to the hydroxyl group of the unsaturated compound, and the isocyanate equivalent/hydroxyl group equivalent ratio is in the range of 0.1 to 1.2. A photosensitive resin containing (b) a photopolymerizable monomer and (c) a sensitizer and/or a sensitizer system that generates free radicals by actinic light. Composition.