JPH11181050A - Acid-pendant type brominated epoxy acrylate and alkali-developing type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel compound that can be suitably used as a resist material for production of multi-layer printed circuit boards, has excellent adhesion to metal plating as copper plating and can provide a self-extinguishing alkali-developing type photosensitive resin composition. SOLUTION: This compound is represented by formula I (X1 -X3 are each H, formula II, formula III where at least two among X1 -X3 are groups other than H; n is 0.3-1.5), typically a compound of' formula V. The objective compound is obtained, for example, by allowing one molecule of acrylic acid to react with one epoxy group where acrylic acid is used in an amount of 0.8-1.1 equivalent per 1 equivalent amount of epoxy group in the brominated epoxy resin, tetraethyl-ammonium bromide is used as a reaction solvent and triphenylphosphine is used as a reaction catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acid pendant type brominated epoxy acrylate, an alkali-developable photosensitive resin composition using the same, and a coated article having the same. More specifically, the present invention relates to a novel acid pendant type brominated epoxy acrylate suitably used for an alkali-developable photosensitive resin composition used for manufacturing a printed wiring board. The present invention relates to an alkali-developable photosensitive resin composition having flammability and excellent in sensitivity, resolution, heat resistance, and stability over time, and a coated product obtained by coating the same on a support.

[0002]

2. Description of the Related Art There is a method of manufacturing a multilayer printed wiring board by forming a via hole using a permanent resist having an epoxy resin skeleton having good electric insulation. In particular, in the surface layer, a method of using a photo-solder resist and plating metal only on a necessary portion has been generally used. As a method of forming a resist pattern on a multilayer printed wiring board, there are a dry film type photoresist and a liquid type photoresist, and various proposals have been made. Such a resist material is required to have various properties such as adhesion to metal plating such as copper, self-flammability, sufficient photocurability (sensitivity), resolution, heat resistance, and stability over time.

As such a resist material, JP-A-61-243869 describes a liquid resist ink composition containing a phenol novolak resin as a main component and developable with an aqueous alkali solution. Also, Japanese Patent Application Laid-Open
JP-A-339356 describes an alkali-developable photosensitive resin composition having a specific photopolymerizable unsaturated compound. JP-A-8-50353 discloses a photosensitive resin composition having a carboxyl group-containing epoxy acrylate. JP-A-8-325339 describes an interlayer electric insulating material for a multilayer printed wiring board having a specific acid pendant rubber-modified halogenated epoxy vinyl ether resin.

[0004] However, in the above various resist materials, novolak resin is used as a skeleton on the main agent side or the hardening agent side to devise heat resistance. However, the viscosity increases rapidly after mixing the main agent and the hardening agent, and There is a problem with stability. In particular, when used as a dry film, the film is wound up into a roll and is not flexible if it contains a novolak skeleton.Therefore, there is a problem that cracks occur when the film is extended from the roll, and there is room for improvement. Was.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel acid pendant brominated epoxy acrylate which is suitably used for a resist material used for manufacturing the above-mentioned multilayer printed wiring board. A further object of the present invention is an alkali-developing photosensitive resin composition having excellent adhesion to metal plating such as copper, having self-flammability, and having excellent sensitivity, resolution, heat resistance, and stability over time, and The purpose is to provide a coating material obtained by coating it on a support. Another object of the present invention is to provide an alkali-developable photosensitive resin composition suitable for use in a dry film form in a resist material used for manufacturing a multilayer printed wiring board, and to coat the same on a support. Providing coatings.

[0006]

As a result of various studies to solve the above-mentioned various problems, the present inventor has found that the object of the present invention can be achieved by the following constitution, and has reached the present invention. (1) An acid pendant brominated epoxy acrylate represented by the following general formula (I).

[0007]

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In the above formula (I), X _{1 to} X ₃ each independently represent a hydrogen atom,

[0009]

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Wherein at least two of X _{1 to} X ₃ represent a group other than a hydrogen atom. n represents 0.3 to 1.5. (2) An alkali-developable photosensitive resin composition comprising an acid pendant brominated epoxy acrylate represented by the general formula (I) described in (1), a photopolymerization initiator, and an epoxy resin. . (3) The alkali-developable photosensitive resin composition according to (2), wherein the epoxy resin is a crystalline epoxy resin. (4) The alkali-developable photosensitive resin composition according to (3), wherein the crystalline epoxy resin is triglycidyl isocyanurate. (5) A coated article, wherein the alkali-developable photosensitive resin composition according to any one of (2) to (4) is coated on a support.

Conventionally, as described above, a resist material used for manufacturing a multilayer printed wiring board includes a dry film type photoresist and a liquid type photoresist. However, the demand for a dry film type resist is increasing because the steps of coating and drying the substrate can be omitted.
However, in general, when such dry film is used, there are problems in adhesion, heat resistance, and the like. In the present invention, the above problem does not occur even when used as a dry film. Further, in the present invention, among the resist materials used for manufacturing a multilayer printed wiring board, particularly excellent effects are obtained when used as a solder resist.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The above general formula (I) in the present invention
In formula ( ₁₎ , at least two of X _{1 to} X ₃ represent a group other than a hydrogen atom, but it is preferable that X ₁ and X ₃ are groups other than a hydrogen atom, and X ₂ is a hydrogen atom.
In addition, n represents a number of 0.3 to 1.5, preferably 0.4 to 1.0, and more preferably 0.5 to 0.8.

The acid pendant type brominated epoxy acrylate of the general formula (I) in the present invention is different from the conventional acid pendant type brominated epoxy acrylate in that the structure and number of the acid to be pendant are selected, and the acid pendant type brominated epoxy acrylate has a repeating structure. By specifying the number n to be relatively small and reducing the molecular weight of the compound to a low molecular weight, the effects of the present invention described above have been successfully obtained. However, for example, n = 0.2
The acid pendant type epoxy acrylate of n = 0.24 was synthesized from the commercially available brominated epoxy of No. 4 and n = 1.5.
Synthesis of acid pendant type epoxy acrylates with n = 1.5 or more from brominated epoxies with more than n = 1.5 and acid pendant type epoxy acrylates with n = 0.3 to 1.5 on average by mixing both. It falls within the scope of the invention.

According to the GPC chart of the acid pendant type epoxy acrylate described later, the resin has a certain molecular weight distribution, and a low molecular weight compound and a high molecular weight compound are mixed, and as a result, n = 0.3-1.
Obviously, if the value falls within the range of 5, almost the same characteristics can be obtained. However, in the above mixing method, at least two kinds of acid pendant epoxy acrylates having different molecular weights must be synthesized, which is not rational.

As a method for producing the acid pendant brominated epoxy acrylate represented by the above general formula (I), basically, one epoxy group is reacted with one molecule of acrylic acid. Acrylic acid is preferably in the range of 0.8 to 1.1 equivalents per equivalent of epoxy group, and it is common to use tetraethylammonium bromide as a reaction solvent and hydroquinone as a polymerization inhibitor. Ammonium is not preferred because it promotes the reaction of the epoxy resin as a curing agent in the later formulation. Here, the use of triphenylphosphine as a reaction catalyst is devised so that the subsequent reaction of the epoxy resin as a curing agent does not proceed at room temperature. However, even if the epoxy resin as a curing agent is a novolak skeleton or a bisphenol A skeleton and has no crystallinity, the epoxy resin dissolves in the system and the reaction proceeds even at room temperature.

Therefore, it is preferable to use a crystalline epoxy resin which is hardly soluble in a solvent as a curing agent from the viewpoint of stability over time. In the present invention, triphenylphosphine is used as a catalyst for the reaction between brominated epoxy resin and tetrabromobisphenol A, and then reacts with acrylic acid.

Next, the alkali-developable photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “composition”) will be described. This composition contains at least the acid pendant brominated epoxy acrylate represented by the general formula (I), a photopolymerization initiator, and an epoxy resin. The content of the acid pendant brominated epoxy acrylate represented by the general formula (I) in the composition of the present invention is not particularly limited, and varies depending on the epoxy equivalent of the epoxy resin as a curing agent. Specifically, the ratio of the carboxyl equivalent of the acid pendant brominated epoxy acrylate represented by the general formula (I) to the epoxy equivalent of the epoxy resin is preferably from 1: 0.8 to 1: 1.2. , Each to the composition. In this range,
No unreacted components remain in the thermosetting reaction in the subsequent step, and the heat resistance is further improved. Specifically, blisters and peeling from the substrate do not occur in the solder heat resistance test at 260 ° C.

The composition of the present invention may contain two or more acid pendant brominated epoxy acrylates represented by the above general formula (I).

Examples of the photopolymerization initiator which can be used in the composition of the present invention include benzoin and its alkyl ether such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl methyl ketal. Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4
Acetophenones such as-(methylthio) phenyl] -2-morpholino-propan-1-one; methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone,
-Anthraquinones such as amylanthraquinone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, benzyl Ketals such as dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and azo compounds, among which acetophenones and thioxanthones are preferable, and both acetophenones and thioxanthone are more preferable. It is preferred to use

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acids such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate It can be used in combination with a photoinitiating auxiliary such as a derivative. The amount of the photopolymerization initiator added to the composition is preferably in proportion to the total number of vinyl groups including the resin of general formula (I) and the photopolymerizable vinyl monomer. It is preferably 1.4 to 2.6% by weight based on the total weight of the total solid content of the product.

The composition of the present invention uses an epoxy resin as a curing system component. As the epoxy resin used in the present invention, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated epoxy resin, biquilenol type epoxy resin, biphenol type Glycidyl ethers such as epoxy resins; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Alicyclic epoxy resins such as 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, etc. Glycidyl esters; tetraglycidyl diaminodiphenylmethane, triglycidyl p- aminophenol, N, glycidyl amines such as N- diglycidyl aniline; 1,3
-Heterocyclic epoxy resins such as -diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate. Among the above epoxy resins, a crystalline epoxy resin is preferable. Thereby, the stability of the composition of the present invention with time is improved, and a composition free from cracks when the composition of the present invention is used for dry film is obtained.
Here, the crystalline epoxy resin is a relatively low-molecular epoxy resin that has almost no molecular weight distribution (the main structure occupies 90% or more) and is solid at room temperature. Since such epoxy resin has crystallinity, it is hardly soluble in solvents,
Therefore, even when the resin is combined with a resin of the general formula (I) having a carboxyl group which is very easily reacted with an epoxy group, the viscosity is less changed with time and the stability is good. Examples of the crystalline epoxy resin include biphenyl-based glycidyl ethers such as YX-4000H manufactured by Yuka Shell Epoxy Co., Ltd., and Y manufactured by Toto Kasei Co., Ltd.
Examples thereof include hydroquinone-based glycidyl ethers such as DC-1312, and triglycidyl isocyanurate.
Among the crystalline epoxy resins, triglycidyl isocyanurate is more preferred because the above effect is more excellent.

In the composition of the present invention, a curing accelerator for epoxy resin can be used. Specific examples of the curing accelerator for epoxy resin include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2ethylimidazole, and 1-cyanoethyl-2. Imidazole compounds such as undecyl imidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-diaminotriazine, 2,4-diamino-6-tolyltriazine, 2,4-diamino-6-xylyl Triazine derivatives such as triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine,
tertiary amines such as m-aminophenol; polyphenols; These curing accelerators can be used alone or in combination.

In the composition of the present invention, the above-mentioned components are dissolved and applied so as to have a viscosity suitable for various coating methods such as screen printing and a roll coater method, and then dried to form a photopolymerizable film. An organic solvent can be used to form.

Examples of the organic solvent used herein include aromatic hydrocarbons such as toluene and xylene; methanol,
Alcohols such as isopropyl alcohol; esters such as ethyl acetate and butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as cellosolve, butyl cellosolve acetate and cellosolve acetate ; Cyclohexanone,
Examples include alicyclic hydrocarbons such as cyclohexanol and petroleum solvents such as petroleum ether and petroleum naphtha.

In screen printing, it is preferable to use a glycol derivative or a petroleum-based solvent which is a high-boiling solvent since the coating process is not particularly continuous. In addition, when screen printing is performed, in particular, the dissolved substance needs to have thixotropic properties, and it is preferable to incorporate a fine particle inorganic filler. The amount of the inorganic filler is 3 to 12 parts by weight per 100 parts by weight of the organic component excluding the solvent.
It is preferably 0 parts by weight, and the viscosity of the solution is preferably 20,000 to 50,000 centipoise in a range where the amount of the organic solvent is 20 to 50% by weight. When a dry film type resist is formed in the present invention, it is preferable to use a low-boiling solvent having a high drying rate in order to improve productivity because the resist is continuously applied and dried.

Further, a photopolymerizable monomer can be added to the composition of the present invention. As such a photopolymerizable vinyl monomer, for example, 2-ethylhexyl (meth)
Such as acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate Esters of (meth) acrylic acid; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) ) Alkoxyalkylene glycol mono (meth) such as acrylate
Acrylates: ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Alkylene polyol poly (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate Triethylene glycol di (meth) acrylate, polyethylene glycol 2
00 di (meth) acrylate, polyethoxylated trimethylolpropane tri (meth) acrylate, polypropoxylated trimethylolpropane tri (meth) acrylate, polyethoxylated bisphenol A di (meth) acrylate, polypropoxylated bisphenol A di (meth)
Acrylate, polyethoxylated hydrogenated bisphenol A di (meth) acrylate, polypropoxylated hydrogenated bisphenol A di (meth) acrylate, polyethoxylated dicyclopentaniel di (meth) acrylate, polypropoxylated dicyclopentaniel di (meth) Polyoxyalkylene glycol poly (meth) acrylates such as acrylates; ester-type poly (meth) acrylates such as neopentyl glycol ester hydroxypivalate di (meth) acrylate; tris [(meth)
Acryloxyethyl] isocyanurate-type poly (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) ) Acrylates, aminoalkyl (meth) acrylates such as t-butylaminoethyl (meth) acrylate; (meth) acrylamide,
(Meth) such as N-methyl (meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine
Acrylamides; vinylpyrrolidone and the like. Of these, acrylates having three or more functional groups are preferred from the viewpoint of excellent heat resistance of the insulating coating film.

The higher the amount of the photopolymerizable monomer in the composition, the better the sensitivity and the resolution. However, if the amount is too large, tackiness occurs and the degree of polymerization increases.
Cracks may occur after development. The amount of the photopolymerizable monomer to be added to the composition is preferably 8 to 20 parts by weight, more preferably 10 to 18 parts by weight, based on 100 parts by weight of the solids in the composition.

In the composition of the present invention, in addition to the above components,
Further various additives as required, for example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide,
Inorganic fillers such as silica and clay; thixotropic agents such as aerosil; coloring agents such as phthalocyanine blue, phthalocyanine green and titanium oxide; silicones, fluorine-based leveling agents and defoamers; polymerization inhibition of hydroquinone and hydroquinone monomethyl ether An agent or the like can be added for the purpose of improving electrical insulation and coating film performance.

The coated article of the present invention has excellent properties as dry film especially in the above-mentioned steps.
Polyethylene terephthalate, polyethylene naphthalate, or the like can be used as a support in the coated article of the present invention. The thickness is preferably 15 to 40 μm.
The support is coated with the above-described alkali-developable photosensitive resin composition of the present invention. The coated article can be obtained by applying the above composition to a support by a screen printing method, an electrostatic coating method, a roll coater method, a curtain coater method, or the like, and drying. The thickness of the composition layer obtained by drying is preferably 20 to 50 μm.

The thus obtained alkali-developable photosensitive resin composition of the present invention is applied on a printed wiring board by a screen printing method, an electrostatic coating method, a roll coater method, a curtain coater method or the like, and dried. Alternatively, after irradiating the photopolymerizable film obtained on the wiring board with a laminator as a dry film with active energy rays such as ultraviolet rays, the unexposed portions are removed with a dilute alkaline aqueous solution to remove the photo-via hole pattern. Can be used to form

Further, the present invention can be used even when a multilayer printed wiring board is formed. Further, it is post-cured by heat to form an interlayer electric insulating layer, then the surface of the insulating layer is roughened with potassium permanganate, subjected to electroless copper plating and electrolytic copper plating, and then laminated with a dry film, Exposure, development, etching, and stripping of the etching resist to form a conductor circuit, and these steps are sequentially repeated to form a multilayer printed wiring board.

[0032]

EXAMPLES Hereinafter, the contents of the present invention will be specifically described using examples, but the contents of the present invention are not limited thereto. Example 1 1) The epoxy equivalent represented by the following structural formula (1) is 400
Of tetrabromobisphenol A type epoxy resin "Epototo YDB-400" (manufactured by Toto Kasei KK, bromine content: 48%) and tetrabromobisphenol A9
9 parts and 4 parts of triphenylphosphine were reacted at 160 ° C. for 1 hour to obtain 503 parts of a brominated epoxy resin having an n number of 0.57 and an epoxy equivalent of 500.

[0033]

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2) 0.06 parts of a polymerization inhibitor hydroquinone was added to the brominated epoxy resin, and 86 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1: 1) was gradually dropped at 120 ° C. After reacting for 8 hours, brominated epoxy vinyl ester 589 having an acid value of 2 g / mg KOH was obtained.
Got a part.

3) Further, 47 parts of toluene was added to and dissolved in the brominated epoxy vinyl ester, 152 parts of tetrahydrophthalic anhydride was added, the mixture was reacted at 90 ° C. for 3 hours, and 135 parts of methyl ethyl ketone was further added for dilution. Thus, 923 parts of a solution (A-1) of an acid value of 77 g / mg KOH of the compound represented by the following structural formula (2) were obtained. Here, n is 0.57. Further, it was confirmed by a GPC chart that the compound obtained by the synthesis was the following structural formula (2) (n = 0.57). That is, the above solution (A-1) was diluted with tetrahydrofuran, and was subjected to high performance liquid chromatography (HLC-802 manufactured by Tosoh Corporation).
0) was used to measure the molecular weight distribution. The GPC chart is shown in FIG. According to the GPC chart, the molecular weight in terms of polystyrene was 1496.6, which almost coincided with the theoretical molecular weight (1476).

[0036]

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4) The following polymerization initiator was completely dissolved in this resin solution (A-1) as shown in the following (formulation) to prepare a main ingredient. Then, as shown in the following (mixing), 119 parts of triglycidyl isocyanurate having an epoxy equivalent of 100.5 (carboxyl group / epoxy group = 1/1)
(TEPIC-S, manufactured by Nissan Chemical Co., Ltd.) and 148 parts of a polyfunctional acrylic monomer, dipentaerythritol hexaacrylate (M-402, manufactured by Toagosei Co., Ltd.), are kneaded using a three-roll mill, and a curing agent is used. Was adjusted.

(Blending) Base agent Resin solution (A-1) 923 parts Polymerization initiator Irgacure 907 (manufactured by Ciba Geigy) 10 parts Polymerization initiator DETX (manufactured by Nippon Kayaku Co., Ltd.) 10 parts Curing agent Epoxy resin TEPIC- S (manufactured by Nissan Chemical Co., Ltd.) 119 parts Acrylic monomer M-402 (manufactured by Toagosei Co., Ltd.) 148 parts

5) Next, after mixing the main agent and the curing agent, a gap 72 μm
m, and coated on a polyethylene terephthalate film (film thickness 20 μm) as a support,
At 0 ° C. × 2 min, a dry film having the resin composition layer having a thickness of 25 μm without tackiness of the coating film was obtained. 6) A glass epoxy copper-clad laminate having a copper foil thickness of 35 μm, which has been immersed in dilute sulfuric acid after polishing with a baffle, is prepared, the solder resist dry film is pressed on the laminate with a hot roll, and then Fuji Photo Film Co., Ltd. ) Made with a positive type step guide pattern film
Irradiation with ultraviolet light of mj / cm ² , then peeling off the polyethylene terephthalate film of the support, and developing using a 1% aqueous solution of sodium carbonate at a liquid temperature of 30 ° C. for 40 seconds resulted in a good pattern having a resolution of 40 μm Was done. Further, the sample was heat-cured at 150 ° C. for 30 minutes in a hot-air circulating drier to obtain a test piece 1-
a was obtained.

7) Specimen 1-a was JIS C-64
According to the test method of No. 81, the soldering was performed in a 260 ° C. solder bath for 10 seconds as one cycle. The subsequent peeling of the resist layer film,
There was no blister state and the heat resistance was good.

8) In addition, the specimen 1-a was subjected to gold plating for 12 minutes at a current density of 1 A / dm ² using “Otronex CI” (gold plating solution manufactured by Celllex, USA). To a thickness of 2 μm. Thereafter, a peeling test was carried out using a cellophane tape, and there was no peeling of the film of the gold plating layer and the resist layer, and the adhesion was good. 9) Further, when the specimen 1-a was subjected to a combustion test, UL-9
It was found to have flame retardancy that passed 4-VO.

Comparative Example 1 1) A tetrabromobisphenol A-type epoxy resin having an epoxy equivalent of 400 "Epototo YDB-400" (manufactured by Toto Kasei Co., Ltd., bromine content: 48%) 400 parts, triphenylphosphine 4 parts, polymerization inhibitor hydroquinone 0.0
While gradually dropping 86 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1: 1) into 6 parts, 8 parts at 120 ° C.
By reacting for an hour, 490 parts of a brominated epoxy vinyl ester having an acid value of 2 g / mg KOH was obtained.

2) Further, 41 parts of toluene was added to and dissolved in the brominated epoxy vinyl ester, 152 parts of tetrahydrophthalic anhydride was added, the mixture was reacted at 90 ° C. for 3 hours, and 123 parts of methyl ethyl ketone was further added for dilution. Thus, 806 parts of a solution (A-2) of an acid value of the compound represented by the structural formula (2) of 85 g / mg KOH was obtained. Here, n is 0.2. Also, the thing obtained by the synthesis is the structural formula (2) (n = 0.2),
It was confirmed by the GPC chart. That is, the solution (A-
2) was diluted with tetrahydrofuran, and the molecular weight distribution was measured using high performance liquid chromatography (HLC-8020 manufactured by Tosoh Corporation). The GPC chart is shown in FIG. According to the GPC chart, the molecular weight in terms of polystyrene was 1294.9, and the theoretical molecular weight (127
It almost coincided with 6).

3) Example 1 was added to this resin solution (A-2).
The following polymerization initiator was completely dissolved in the same manner as in (1) to prepare a main component (formulation is shown below). Then the epoxy equivalent is 10
119 parts of triglycidyl isocyanurate of 0.5 (carboxyl group / epoxy group = 1/1) (epoxy resin T
EPIC-S, manufactured by Nissan Chemical Co., Ltd.) and 148 parts of a polyfunctional acrylic monomer, dipentaerythritol hexaacrylate (M-402, manufactured by Toagosei Co., Ltd.), are kneaded using a three-roll mill to obtain a curing agent. Adjusted (formulation is shown below).

(Blend) 806 parts Polymerization initiator Irgacure 907 (manufactured by Ciba Geigy) 10 parts Polymerization initiator DETX (manufactured by Nippon Kayaku Co., Ltd.) 10 parts Curing agent Epoxy resin TEPIC- S (manufactured by Nissan Chemical Co., Ltd.) 119 parts Acrylic monomer M-402 (manufactured by Toagosei Co., Ltd.) 148 parts

4) Next, after mixing the main agent and the curing agent, a gap of 72 μm was measured using a film forming device Coma Doctor.
m, coated on a polyethylene terephthalate film as a support, and dried at 100 ° C. for 2 minutes. The resulting dry film had a sticky coating, and the peelability from the support after irradiation with ultraviolet rays was low. I couldn't proceed to the next step.

Comparative Example 2 1) 400 parts of tetrabromobisphenol A-type epoxy resin "Epototo YDB-400" having an epoxy equivalent of 400 (manufactured by Toto Kasei Co., Ltd., bromine content: 48%), 576 parts of tetrabromobisphenol A and 4 parts of triphenylphosphine By reacting at 160 ° C. for 1 hour, n
980 parts of a brominated epoxy resin having a number of 2.17 and an epoxy equivalent of 976 were obtained. 2) To the brominated epoxy resin, 0.06 part of a polymerization inhibitor hydroquinone was added, and the mixture was reacted at 120 ° C. for 8 hours while gradually adding 86 parts of acrylic acid (the number of epoxy groups: the number of carboxyl groups = 1: 1) dropwise. By doing, acid value 2g / mgK
1066 parts of a brominated epoxy vinyl ester of OH were obtained. 3) Further, 64 parts of toluene was added to and dissolved in the brominated epoxy vinyl ester, 152 parts of tetrahydrophthalic anhydride was added, reacted at 90 ° C. for 3 hours, and further diluted with 244 parts of methyl ethyl ketone.
1,526 parts of a solution (A-3) of an acid value of 37 g / mg KOH of the compound of the structural formula (2) were obtained. Here, n is 2.17. Further, it was confirmed by a GPC chart that the product obtained by the synthesis was the structural formula (2) (n = 2.17). That is, the solution (A-3) was diluted with tetrahydrofuran, and the molecular weight distribution was measured using high performance liquid chromatography (HLC-8020 manufactured by Tosoh Corporation). The GPC chart is shown in FIG. According to the GPC chart, the molecular weight in terms of polystyrene was 24.
55.8, which was almost the same as the theoretical molecular weight (2436).

4) Example 1 was added to this resin solution (A-3).
Similarly to the above, the following polymerization initiator was completely dissolved to prepare a main component (the composition is shown below). Then the epoxy equivalent is 10
0.5 part of triglycidyl isocyanurate (carboxyl group / epoxy group = 1/1) (epoxy resin TE
PIC-S (manufactured by Nissan Chemical Co., Ltd.)) and 13 parts of polyfunctional acrylic monomer dipentaerythritol hexaacrylate (M-402 (manufactured by Toagosei Co., Ltd.)) are kneaded using a three-roll mill and cured. The agent was prepared (formulation is shown below).

(Blending) Main agent Resin solution (A-3) 1526 parts Polymerization initiator Irgacure 907 (manufactured by Ciba Geigy) 10 parts Polymerization initiator DETX (manufactured by Nippon Kayaku Co., Ltd.) 10 parts Curing agent Epoxy resin TEPIC- S (manufactured by Nissan Chemical Co., Ltd.) 119 parts Acrylic monomer M-402 (manufactured by Toagosei Co., Ltd.) 148 parts

5) Next, after mixing the main agent and the curing agent, a gap 72 μm
m, and applied on a polyethylene terephthalate film as a support. A dry film of the resin having a thickness of 25 μm with no tackiness was obtained at a drying condition of 100 ° C. for 2 minutes.

6) A glass epoxy copper-clad laminate having a copper foil thickness of 35 μm, which was immersed in dilute sulfuric acid after polishing with a baffle, was prepared, the solder resist dry film was pressed on the laminate with a hot roll, and then Fuji Photo A pattern film of a positive type step guide manufactured by Film Co., Ltd. is adhered to the film and irradiated with ultraviolet rays of 300 mj / cm ² , then the polyethylene terephthalate film of the support is peeled off, and a 1% aqueous solution of sodium carbonate at a liquid temperature of 30 ° C. No development was possible at all even after 5 minutes of development.

Embodiment 2 FIG. 1) Novolac type epoxy resin 261 having an epoxy equivalent of 206 was used as a curing agent, using the main agent prepared in Example 1.
(Carboxyl group / epoxy group = 1/1) (epoxy resin YDCN-704 (manufactured by Toto Kasei Co., Ltd.)) and dipentaerythritol hexaacrylate of a polyfunctional acrylic monomer (M-402 (manufactured by Toagosei Co., Ltd.)) ) 148 parts were stirred and dissolved in 104 parts of methyl ethyl ketone as a solvent to prepare a curing agent (formulation is shown below).

(Blending) Main agent Resin solution (A-1) 923 parts Polymerization initiator Irgacure 907 (manufactured by Ciba Geigy) 10 parts Polymerization initiator DETX (manufactured by Nippon Kayaku Co., Ltd.) 10 parts Curing agent Epoxy resin YDCN- 704 (manufactured by Toto Kasei Co., Ltd.) 261 parts Acrylic monomer M-402 (manufactured by Toagosei Co., Ltd.) 148 parts Methyl ethyl ketone 104 parts

2) Next, after mixing the main agent and the curing agent, a gap 77 μm
m, and applied on a polyethylene terephthalate film as a support. A dry film of the resin composition was obtained at a drying condition of 100 ° C. × 2 min and having a thickness of 25 μm with no tackiness of the coating film. The viscosity doubled with time, and it was found that it was difficult to produce a dry film having a uniform thickness. In 5) of Example 1 above, a mixture containing the main agent and the curing agent was also observed for 3 hours or more in the same manner as above, but the viscosity did not change, and even after 3 hours, a uniform dry film was obtained.

Comparative Example 3 1) A solder resist dry film KM manufactured by Morton International Co., Ltd. was pressed with a hot roll onto a glass epoxy copper-clad laminate having a copper foil thickness of 35 μm prepared in the same manner as in the example, and then manufactured by Fuji Photo Film Co., Ltd. Adhere the pattern film of the positive type step guide to 300mj / c
irradiated with ultraviolet rays of m ^2, then peeled off the polyethylene terephthalate film support, a result of the development in using 1% aqueous sodium carbonate solution temperature of 30 ° C. 40 seconds, resolution 4
A good pattern of 0 μm was obtained. Further, the sample was heat-cured at 150 ° C. for 30 minutes using a hot-air circulation dryer to obtain a test piece 1-b.

2) Next, using "Autolonex CI" (a gold plating solution manufactured by Celllex, USA),
b was subjected to gold plating at a current density of 1 A / dm ² for 12 minutes, gold was applied to a thickness of 2 μm, and a peeling test was performed using a cellophane tape. As a result, the resist layer was peeled off from the substrate surface. This is probably because the plating solution had penetrated between the lower substrate surface and the resist layer from the pattern portion.

[0057]

According to the present invention, it is possible to provide a novel acid pendant type brominated epoxy acrylate suitably used for an alkali developing type photosensitive resin composition used for manufacturing a printed wiring board. Excellent adhesion, self-flammability, sensitivity, resolution, heat resistance,
Alkaline development type photosensitive resin composition excellent in aging stability,
And a coating product obtained by coating it on a support.

[Brief description of the drawings]

FIG. 1 is a diagram showing a GPC chart of an acid pendant type brominated epoxy acrylate of the present invention synthesized in Example 1.

FIG. 2 is a diagram showing a GPC chart of an acid pendant brominated epoxy acrylate synthesized in Comparative Example 1.

3 shows a GPC chart of an acid pendant brominated epoxy acrylate synthesized in Comparative Example 2. FIG.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 515 515 H05K 3/06 H05K 3/06 H 3/46 3/46 T

Claims (5)

[Claims] 1. An acid pendant brominated epoxy acrylate represented by the following general formula (I). Embedded image In the above formula (I), X _{1 to} X ₃ each independently represent a hydrogen atom, Wherein at least two of X _{1 to} X ₃ represent a group other than a hydrogen atom. n represents 0.3 to 1.5. 2. An alkali-developing photosensitive resin composition comprising the acid pendant brominated epoxy acrylate represented by the general formula (I) according to claim 1, a photopolymerization initiator, and an epoxy resin. Stuff. 3. The alkali-developable photosensitive resin composition according to claim 2, wherein the epoxy resin is a crystalline epoxy resin. 4. The alkali-developable photosensitive resin composition according to claim 3, wherein the crystalline epoxy resin is triglycidyl isocyanurate. 5. A coated article, wherein the alkali-developable photosensitive resin composition according to claim 2 is coated on a support.