JPH10186653A - Flame retardant alkali-developable photosensitive resin composition and built-up multilayred circuit board using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant alkali-developable photosensitive resin compn. capable of producing a built-up multiayered circuit board having satisfactory flame resistance with high productivity at a low cost in a satisfactory working environment and to obtain a built-up multilayred circuit board using the compsn. SOLUTION: This flame retardant alkali-developable photosensitive resin compsn. contains 100 pts.wt. photopolymerizable unsatd. compd. having 30-180 mgKOH/g acid value represented by the formula, 5-50 pts.wt. epoxy compd. and 0.1-30 pts.wt. photopolymn. initiator or sensitizer as essential components and has 5-30wt.% bromine content. In the formula, R1 is H or methyl, X is H or a monovalent residue of a polybasic acid anhydride, Y is a divalent residue of a polybasic acid anhydride and (n) is an integer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant alkali-developable photosensitive resin composition using a photopolymerizable unsaturated compound containing a bromine atom, and more particularly to an interlayer insulating material for a build-up multilayer substrate. Also, the present invention relates to a flame-retardant alkali-developable photosensitive resin composition suitably used as a permanent insulating protective film of a printed wiring board, and a build-up multilayer substrate using the same.

[0002]

2. Description of the Related Art In recent years, electronic devices and computers have been required to be smaller and more sophisticated than before, and accordingly, components used at higher densities have been required. ing. For example, in printed wiring boards, circuit miniaturization and multilayering are being promoted in order to improve the wiring density per unit volume. It has been proposed and put into practical use. The feature of this build-up multilayer substrate is that, instead of the through hole conventionally used for interlayer conduction of the multilayer substrate, interlayer conduction is performed via an internal via hole, and this internal via hole is provided in an insulating layer. As a method, two methods, a laser method and a photolithography method, are mainly studied.

[0003] As a method of forming a via hole using a laser, for example, Japanese Patent Application Laid-Open Nos. 58-64097 and 61-96792 are disclosed. However, there is a disadvantage that productivity is low due to the low speed, and a dedicated facility is newly required, resulting in high cost. On the other hand, examples of a photosensitive resin material used in a photolithography method include, for example, Japanese Patent Application Laid-Open No. 5-339.
No. 356, Japanese Patent Application Laid-Open No. 6-237094, Japanese Patent Publication No. 8-3633, and the like are disclosed. These methods allow the simultaneous drilling of via holes and allow the use of conventional printed wiring board manufacturing facilities as they are,
There is a merit that higher productivity and lower cost can be expected as compared with the laser method. However, currently used materials are of a type that can be developed with an organic solvent, and therefore have problems such as deterioration of the working environment and insufficient flame retardancy. hard.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-productivity, low-cost, flame-retardant multi-layer wiring board having sufficient flame retardancy under a favorable working environment. It is an object of the present invention to provide an alkali developing photosensitive resin composition and a build-up multilayer wiring board using the same.

[0005]

Means for Solving the Problems In order to solve such problems, the present inventors have synthesized various carboxyl group-containing photopolymerizable unsaturated compounds based on epoxy acrylates, and As a result of using the epoxy compound with an epoxy compound, the object of the present invention was achieved by using a carboxyl group-containing photopolymerizable unsaturated compound mainly composed of epoxy acrylate containing a bromine atom and a compound having an epoxy group. We have found what we can do and completed the present invention.

That is, the present invention provides, as an essential component, a compound represented by the following general formula (1) and having an acid value of 30 to 180 mg:
100 parts by weight of a photopolymerizable unsaturated compound that is KOH / g,
A flame-retardant alkali-developable photosensitive resin composition containing 5 to 50 parts by weight of an epoxy compound and 0.1 to 30 parts by weight of a photopolymerization initiator or a sensitizer and having a bromine content of 5 to 30% by weight. Things.

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, X is a hydrogen atom or a monovalent polybasic anhydride residue represented by the following general formula (2), and Y is the following general formula (3) Any of divalent polybasic acid anhydride residues represented by

Embedded image (Wherein, R ₂ , R ₃ , and R ₄ each represent a divalent, trivalent, or tetravalent organic group)

Embedded image (Wherein, R ₂ , R ₃ , and R ₄ each represent a divalent, trivalent, or tetravalent organic group)

[0007] The present invention is also a build-up multilayer wiring board prepared using the above flame-retardant alkali-developable photosensitive resin composition.

Hereinafter, the flame-retardant alkali-developable photosensitive resin composition of the present invention (hereinafter referred to as photosensitive resin composition) will be described. First, the photosensitive resin composition of the present invention is blended with a photopolymerizable unsaturated compound represented by the above general formula (1) (hereinafter, also referred to as component A) as an essential component. Here, n in the general formula (1) is preferably 20 or less. When n exceeds 20, development with an alkaline aqueous solution becomes difficult.

The component A comprises a brominated bisphenol A type epoxy (meth) acrylate compound and the above-mentioned X (monovalent polybasic acid anhydride residue) and Y (divalent polybasic acid anhydride residue). Obtained as a reaction product with the given acid anhydride.

Examples of the acid anhydride for introducing these polybasic acid anhydride residues into the component A include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and tetrahydrophthalic anhydride. Hexahydrophthalic acid,
Methylendomethylenetetrahydrophthalic anhydride,
Chlorendic anhydride, methyltetrahydrophthalic anhydride,
Polybasic anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bistrimellitate dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride And the like. These polybasic acid anhydrides may be used alone or in combination of two or more.

The acid value of the component A is 30 to 180 mg.
KOH / g, preferably 50-100 mg KOH / g. If the acid value of the component A is greater than 180 mgKOH / g, the alkali resistance and electrical properties of the cured film will deteriorate,
If it is smaller than gKOH / g, the solubility in an alkaline aqueous solution is deteriorated, so that the resolution is reduced.

The component A can be produced as follows. First, a brominated bisphenol A type epoxy (meth) acrylate compound is synthesized by reacting a brominated bisphenol A type epoxy compound synthesized from brominated bisphenol A with (meth) acrylic acid. Then, a brominated bisphenol A type epoxy (meth) acrylate compound can be produced by reacting with the above-mentioned acid anhydride mixture giving X and Y, respectively. At this time, the reaction may be performed at a reaction temperature of 100 to 130 ° C, preferably 110 to 120 ° C, in the presence of a solvent such as ethyl cellosolve acetate or butyl cellosolve acetate.

The photosensitive resin composition of the present invention contains an epoxy compound (hereinafter, also referred to as a component B) as an essential component. Examples of the B component include epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, and bromides thereof. And epoxy compounds having at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. These epoxy compounds may be used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention includes:
As an essential component, a photopolymerization initiator or a sensitizer (hereinafter, also referred to as a component C) is blended. The C component is used not only as the A component but also as a photopolymerization initiator for a photopolymerizable unsaturated compound having an ethylene bond which is added as necessary. As the components, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone,
Acetophenones such as trichloroacetophenone and p-tert-butylacetophenone; benzophenone;
Benzophenones such as -chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl dimethyl ketal, thioxanthone and 2-chlorothioxane Son, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2
Sulfur compounds such as -isopropylthioxanthone, 2
Anthraquinones such as -ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide and cumene peroxide; 2-mercaptobenzimidazole , 2-mercaptobenzoxazole, 2-
And thiol compounds such as mercaptobenzothiazole. These photopolymerization initiators or sensitizers may be used alone or in combination of two or more.

Further, a compound which does not act as a photopolymerization initiator by itself, but which can increase the ability of the photopolymerization initiator by using it in combination with the above-mentioned compound as the component C can be blended. . Examples of such a compound include a tertiary amine such as triethanolamine which is effective when used in combination with benzophenone.

The photosensitive resin composition of the present invention comprises, as essential components, A component, B component and C component. The mixing ratio of each component is 100 parts by weight of A component and B component is 100 parts by weight. 5 to 50 parts by weight, preferably 10 to 30 parts by weight, and component C is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight. If the blending ratio of the component B is less than 5 parts by weight with respect to 100 parts by weight of the component A, the properties of the cured product of the photosensitive resin composition of the present invention, particularly the alkali resistance becomes insufficient. Since the solubility in an aqueous alkali solution is reduced, the developability is deteriorated. A component 100
When the blending ratio of the component C to the parts by weight is less than 0.1 parts by weight, the photopolymerization speed is low, and the sensitivity is lowered. on the other hand,
If the amount exceeds 30 parts by weight, light hardly reaches the bottom of the resin layer, so that photopolymerization becomes insufficient, which causes adverse effects such as a decrease in development margin and insufficient adhesion to the substrate.

Further, the photosensitive resin composition of the present invention has a bromine content of 5 to 30% by weight, preferably 10 to 25% by weight. If the bromine content in the photosensitive resin composition is less than 5%, sufficient flame retardancy will not be exhibited, and if it is more than 30%, problems such as blistering of the plating film tend to occur.

The photosensitive resin composition of the present invention may contain other photopolymerizable unsaturated compounds in addition to the essential component A, depending on the purpose of use. Other photopolymerizable unsaturated compounds include halogenated bisphenol A type epoxy (meth) acrylate compounds other than brominated bisphenol A type epoxy (meth) acrylate compounds, and non-halogenated bisphenol A type epoxy (meth) acrylate Compounds and the like are included, and the mixing ratio of these compounds is 50 parts by weight or less based on 100 parts by weight of the component A. If it exceeds 50 parts by weight, a problem arises in tackiness after pre-curing.

Examples of such a photopolymerizable unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Monomers having a hydroxyl group such as -ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) ) Acrylates such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate And the like. In addition, these halides (excluding brominated bisphenol A type epoxy (meth) acrylate compounds)
It may be. These compounds may be one kind,
Two or more types may be used in combination.

The photosensitive resin composition of the present invention may further comprise an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent, a defoaming agent, if necessary, in addition to the above-mentioned essential components. An additive such as an extender or a compounding agent such as an organic solvent may be blended. The type and amount of such additives and compounding agents may be appropriately selected within a range that does not impair the properties of the photosensitive resin composition of the present invention.

Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids,
Phenols, quaternary ammonium salts, methylol group-containing compounds and the like, and by heating the coating film in combination with a small amount of these, the heat resistance of the insulating film obtained,
Various properties such as solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, and hardness can be improved.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, and phenothiazine. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the leveling agent include silicon-based, fluorine-based, and acrylic-based compounds. Examples of the extender include silica, alumina, talc, calcium carbonate, clay, and aerosil. Each of these may be used alone or in combination of two or more.

[0023]

Next, a method for using the photosensitive resin composition of the present invention will be described. First, to the photosensitive resin composition of the present invention containing at least essential components, a suitable photopolymerization initiator, sensitizer, curing accelerator, additives such as extender pigment, and kneaded with a three-roll mill or the like. Prepare a photosensitive resist ink. Next, this resist ink is applied on a substrate by any method such as screen printing, and then precured to evaporate the solvent and make the coating film tack-free. After the pre-curing, a desired mask pattern is placed in a contact (contact) or off-contact (non-contact) state, placed on the substrate on which the coating film of the composition is formed, and irradiated with ultraviolet light from a light source.

The light source suitable for photocuring the photosensitive resin composition of the present invention includes, for example, an ultraviolet lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp. Further, the photosensitive resin composition of the present invention can be cured not only by light but also by heat.

The components of the composition coating film in the region exposed to the ultraviolet light are cross-linked by photopolymerization to become insoluble. Next, by removing the non-exposed area using an alkaline aqueous solution, a desired developed pattern is obtained. Examples of the developer suitable for alkali developing the photosensitive resin composition of the present invention include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, and an aqueous solution of an alkali metal hydroxide. In particular, development can be efficiently performed using a weakly alkaline aqueous solution of about 0.1 to 10% by weight of an alkali metal carbonate such as sodium carbonate, potassium carbonate, lithium carbonate or the like. This alkali development may be performed at 10 to 50 ° C, preferably 20 to 40 ° C, using a commercially available developing machine.

In order to improve the corrosion resistance after the alkali development, it is preferable to perform a curing treatment by heating. The photosensitive resin composition of the present invention, by performing a heat treatment, not only significantly improves the durability against strong alkaline water, but also the printed wiring board such as adhesion to metals such as copper, heat resistance and surface hardness. The various properties required for the material are also improved. The heating temperature under these heat curing conditions is 100 to 20.
The heating time may be about 0 ° C. and about 10 minutes to 2 hours. Further, ultraviolet irradiation may be performed instead of the heat treatment.

Solvents suitable for preparing the solution of the photosensitive resin composition of the present invention include ketones such as methyl ethyl ketone and methyl isobutyl ketone, and cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and cellosolve acetate. And carbitols such as carbitol acetate.

By forming a signal wiring by electroless plating or the like on the pattern having an improved coating film strength in this way, and further by plating the inner surface of the via hole, a printed wiring having excellent heat resistance and flame retardancy is obtained. You can get a board.

[0029]

The present invention will be specifically described below based on Synthesis Examples, Examples and Comparative Examples.

Synthesis Example 1 200 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 (bromine content: 49%) was dissolved in butyl cellosolve acetate, and 37 g of acrylic acid, 0.35 g of benzyltriethylammonium chloride and 75 mg of hydroquinone were added. 90 ~ while blowing air
The reaction was performed at 100 ° C. for 10 hours. 52 g of ethylene glycol bistrimellitate dianhydride was added to the obtained resin solution,
17 g of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted at 110 to 120 ° C. for 5 hours to obtain an acid value of 75 mg.
A resin solution of KOH / g (solid content) was obtained. FIG. 1 shows the infrared absorption spectrum (IR) of the coating film obtained by drying the obtained resin solution.

Synthesis Example 2 200 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 (bromine content: 49%) was dissolved in butyl cellosolve acetate, 37 g of acrylic acid, 0.35 g of benzyltriethylammonium chloride and 75 mg of hydroquinone were added. 90 ~ while blowing air
The reaction was performed at 100 ° C. for 10 hours. 25 g of ethylene glycol bistrimellitate dianhydride was added to the obtained resin solution,
8 g of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted at 110 to 120 ° C. for 5 hours to obtain an acid value of 41 mgK.
An OH / g (solid content) resin solution was obtained.

Synthesis Example 3 200 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 (bromine content: 49%) was dissolved in butyl cellosolve acetate, and 37 g of acrylic acid, 0.35 g of benzyltriethylammonium chloride and 75 mg of hydroquinone were added. 90 ~ while blowing air
The reaction was performed at 100 ° C. for 10 hours. 15 g of ethylene glycol bistrimellitate dianhydride was added to the obtained resin solution,
5 g of 1,2,3,6-tetrahydrophthalic anhydride was added and reacted at 110 to 120 ° C. for 5 hours to obtain an acid value of 26 mgK.
An OH / g (solid content) resin solution was obtained.

Synthesis Example 4 200 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 (bromine content: 49%) was dissolved in butyl cellosolve acetate, and 37 g of acrylic acid, 0.35 g of benzyltriethylammonium chloride and 75 mg of hydroquinone were added. 90 ~ while blowing air
The reaction was performed at 100 ° C. for 10 hours. Ethylene glycol bis trimellitate dianhydride 110 was added to the obtained resin solution.
g, 1,2,3,6-tetrahydrophthalic anhydride 40 g
And reacted at 110 to 120 ° C. for 5 hours to obtain an acid value of 13
A resin solution of 0 mgKOH / g (solid content) was obtained.

Synthesis Example 5 200 g of a brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 (bromine content: 49%) was dissolved in butyl cellosolve acetate, and 37 g of acrylic acid, 0.35 g of benzyltriethylammonium chloride and 75 mg of hydroquinone were added. 90 ~ while blowing air
The reaction was performed at 100 ° C. for 10 hours. Ethylene glycol bistrimellitate dianhydride 220 was added to the obtained resin solution.
g, 1,2,3,6-tetrahydrophthalic anhydride 80 g
And reacted at 110 to 120 ° C. for 5 hours to obtain an acid value of 18
A resin solution of 7 mgKOH / g (solid content) was obtained.

Synthesis Example 6 112 g of a bisphenol A type epoxy resin having an epoxy equivalent of 450 was dissolved in butyl cellosolve acetate, 19 g of acrylic acid, 0.17 g of benzyltriethylammonium chloride and 40 mg of hydroquinone were added, and the mixture was blown with air at 90 to 100 ° C. The reaction was performed for 10 hours. 30 g of ethylene glycol bistrimellitate dianhydride and 10 g of 1,2,3,6-tetrahydrophthalic anhydride are added to the obtained resin solution and reacted at 110 to 120 ° C. for 5 hours to obtain an acid value of 78 mgKOH / g (solid content). Value) was obtained.

Example 1 100 parts by weight of the resin obtained in Synthesis Example 1 (as solid content), 45 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 180, and 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate Part, photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-
5 parts by weight of 1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, mixed and dispersed using a three-roll mill, and then mixed with a photosensitive resin. Composition (bromine content 19
%). Next, this composition was applied on a copper-clad laminate and precured at 60 ° C. for 1 hour to form a 40 μm-thick photosensitive layer having no tack at room temperature. Then, using an ultra-high pressure mercury lamp, a negative mask on which a via hole pattern having a diameter of 30 to 200 μm is drawn is adhered to 500 mj / c.
m ² ultraviolet rays, sprayed with a 1% aqueous solution of sodium carbonate at 30 ° C. for 2 minutes, and developed.
To obtain a coating film cured by after-curing for 60 minutes.

Example 2 45 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 180 and 100 parts by weight of a resin (as a solid content) obtained in Synthesis Example 4 and 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate Part, photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-
5 parts by weight of 1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, mixed and dispersed using a three-roll mill, and then mixed with a photosensitive resin. Composition (bromine content 15
%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Example 3 45 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 180 and 100 parts by weight of a resin (as a solid content) obtained in Synthesis Example 2 and 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate Part, photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-
5 parts by weight of 1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, mixed and dispersed using a three-roll mill, and then mixed with a photosensitive resin. Composition (bromine content 22
%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Example 4 A phenol novolak type epoxy resin 45 having an epoxy equivalent of 180 was added to 40 parts by weight of the resin (as solid content) obtained in Synthesis Example 1 and 60 parts by weight of the resin (same as above) obtained in Synthesis Example 6.
Parts by weight, 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate, a photopolymerization initiator 2,2-
5 parts by weight of dimethoxy-1,2-diphenylethan-1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, and a three-roll mill was added. To obtain a photosensitive resin composition (bromine content: 8%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Comparative Example 1 To 100 parts by weight of the resin (as solid content) obtained in Synthesis Example 5, 45 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 180, and 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate Part, photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-
5 parts by weight of 1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, mixed and dispersed using a three-roll mill, and then mixed with a photosensitive resin. Composition (bromine content 11
%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Comparative Example 2 To 100 parts by weight of the resin (as solid content) obtained in Synthesis Example 3, 45 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 180, and 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate Part, photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-
5 parts by weight of 1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, mixed and dispersed using a three-roll mill, and then mixed with a photosensitive resin. Composition (bromine content 23
%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Comparative Example 3 A phenol novolak type epoxy resin 45 having an epoxy equivalent of 180 was added to 20 parts by weight of the resin (solid content) obtained in Synthesis Example 1 and 80 parts by weight of the resin (same as above) obtained in Synthesis Example 6.
Parts by weight, 10 parts by weight of a photopolymerizable unsaturated compound dipentaerythritol hexaacrylate, a photopolymerization initiator 2,2-
5 parts by weight of dimethoxy-1,2-diphenylethan-1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle diameter of 5 μm were added, and a three-roll mill was added. To obtain a photosensitive resin composition (bromine content: 4%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Comparative Example 4 75 parts by weight of a brominated phenol novolak-type epoxy resin having an epoxy equivalent of 310 (bromine content: 41%) was added to 100 parts by weight of the resin (as a solid content) obtained in Synthesis Example 1; 10 parts by weight of a saturated compound dipentaerythritol hexaacrylate, a photopolymerization initiator 2,2-dimethoxy-
5 parts by weight of 1,2-diphenylethan-1-one, 8 parts by weight of an epoxy curing agent 2-ethyl-4-methylimidazole and 5 parts by weight of calcium carbonate fine powder having an average particle size of 5 μm were added, and the mixture was rolled using a three-roll mill. The mixture was dispersed to obtain a photosensitive resin composition (bromine content: 32%). Next, using this, exposure and development were performed in the same manner as in Example 1, and after-curing to obtain a cured coating film.

Various samples obtained in the above Examples and Comparative Examples were evaluated for flame retardancy, resolution, migration characteristics and chemical resistance. Examples 1 to 4
After roughening the surfaces of the various cured coating films obtained in Comparative Examples 1 to 4 using an alkali solution of potassium permanganate, copper having a thickness of about 30 μm is formed by electroless copper plating or electrolytic copper plating. A build-up two-layer substrate having a plating layer formed on the entire surface was prepared. The obtained two-layer substrate is 10 mm
A solder heat resistance test was performed using a test piece cut to × 10 mm. Further, the volume resistivity was measured using a sample obtained by etching the copper plating layer of the two-layer substrate to form an electrode. Table 1 shows the test results. In addition, various physical property data were measured on condition of the following.

(1) Flame Retardancy The after-cured coating film was peeled off from the copper-clad laminate and used as a test piece, and measured according to UL standards. V-0: Burning time within 10 seconds at maximum, average 5 Within seconds V-1: Burning time within 30 seconds at maximum, within 25 seconds on average HB: Burn out

(2) Resolution Minimum diameter (μm) of a via hole developable at a coating thickness of 40 μm

(3) Migration Characteristics A test piece having a photosensitive resin layer of about 40 μm was formed on a comb-shaped electrode pattern having a line interval of 0.15 mm formed on a glass epoxy substrate having a copper foil thickness of 18 μm. 121
The temperature was set in an unsaturated pressure cooker tester set at a temperature of 85 ° C., 85% RH, and 50 V DC, and the change over time (initial resistance and resistance after 300 hours) of the voltage applied between the electrodes was measured.

(4) Chemical Resistance After exposure and development, the coating film heated at 160 ° C. for 60 minutes was
It was immersed in the following chemicals under the following conditions, and the appearance after immersion was evaluated. Acid resistance 5% HCl 24 hours Alkali resistance 5% NaOH 24 hours immersion Solvent resistance NMP 40 ° C-10 minutes (NMP: N-
(Methyl-pyrrolidone) ：: No abnormality is found in the coating film ×: An abnormality is found in the coating film

(5) Solder heat resistance The test piece, which had been absorbed for 96 hours at 40 ° C. and 90% relative humidity, was immersed in a solder bath at 260 ° C. for 10 seconds, and the state of swelling and crack generation (in 10 test pieces) Number of occurrences).

(6) Volume resistivity Implemented in accordance with JIS C6481. The measurement was carried out under normal conditions and at 40 ° C./relative humidity 90% / after absorbing moisture for 96 hours.

[0051]

[Table 1]

[0052]

The photosensitive resin composition of the present invention can be developed with an aqueous alkali solution having little adverse effect on the human body,
It is a photosensitive resin composition having excellent heat resistance, resolution, chemical resistance, acid resistance and alkali resistance, and having flame retardancy. Therefore, when the photosensitive resin composition of the present invention is used, a build-up multilayer wiring board having a sufficient flame retardancy can be produced at a high productivity and at a low cost under a favorable working environment. It is also a promising material for use in permanent protective films such as solder resists having properties.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a brominated epoxy acrylate anhydride adduct synthesized in Synthesis Example 1.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/028 G03F 7/028 H05K 3/28 H05K 3/28 D 3/46 3/46 T // C09D 4/02 C09D 4/02 ( 72) Inventor Chiaki Asano 3-6-16 Kasumi, Narashino-shi, Chiba (72) Inventor Hideyasu Togane 2-25 Nishi Mizue, Edogawa-ku, Tokyo

Claims (5)

[Claims] 1. As an essential component, 100 parts by weight of a photopolymerizable unsaturated compound represented by the following general formula (1) and having an acid value of 30 to 180 mg KOH / g, and an epoxy compound of 5 to 50
A flame-retardant alkali-developable photosensitive resin composition comprising 0.1 parts by weight of a photopolymerization initiator or a sensitizer and having a bromine content of 5 to 30% by weight. Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, X is a hydrogen atom or a monovalent polybasic anhydride residue represented by the following general formula (2), and Y is the following general formula (3) Any of divalent polybasic acid anhydride residues represented by the formula: n represents an integer of 0 or more. (In the formula, R ₂ , R ₃ , and R ₄ each represent a divalent, trivalent, or tetravalent organic group.) (Wherein, R ₂ , R ₃ , and R ₄ each represent a divalent, trivalent, or tetravalent organic group) 2. The flame-retardant alkali-developable photosensitive resin composition according to claim 1, wherein n in the general formula (1) is 20 or less. 3. The photopolymerizable unsaturated compound according to claim 1, wherein the brominated bisphenol A type epoxy (meth) acrylate compound is mixed with ethylene glycol bistrimellitate dianhydride and 1,2,3,6-tetrahydroanhydride. 3. The flame-retardant alkali-developable photosensitive resin composition according to claim 1, which is a reaction product with phthalic anhydride. 4. The photopolymerizable unsaturated compound 1 according to claim 1,
3. The flame-retardant alkali-developable photosensitive resin composition according to claim 1, wherein 50 parts by weight or less of a photopolymerizable unsaturated compound other than the compound represented by the general formula (1) is added to 00 parts by weight. Stuff. 5. A build-up multilayer wiring board prepared using the flame-retardant alkali-developable photosensitive resin composition according to claim 1.