JPH0635191A - Photosensitive resin composition and production of photosensitive element and plating resist using same - Google Patents

Abstract

PURPOSE:To improve resolution, alkali developing property, plating resistance and low contamination property of a plating liquid by incorporating a specified unsatd. polymer compd., photopolymerizable unsatd. compd., and photoinitiator. CONSTITUTION:This compsn. consists of an unsatd. polymer compd., photopolymerizable unsatd. compd. having at least two ethylene groups at the molecular end, and photoinitiator which produces free radicals by irradiation of active rays. The unsatd. polymer compd. is prepared by copolymerizing 10-90 pts.wt of vinyl monomers (a) and 10-90 pts.wt. of maleic acid anhydride (b), with total 100 pts.wt. of (a) and (b), and then allowing a compd. expressed by formula II to react with this copolymer compd. in the equiv. ratio of 0.1-1.2 hydroxyl group/acid anhydride. formulae I and II, R1 is hydrogen atom or methyl group, R2-R4 is hydrogen atoms, alkyl groups of 1-4 carbon number, halogen atoms, etc., R5-R7 are hydrogen atom or methyl group, R8 is an alkylene group of 1-8 carbon number or benzene ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a photosensitive element using the same and a method for producing a plating resist. More specifically, in the production of printed wiring boards and the like, an alkali-developable photosensitive resin composition having excellent properties that can be used as a resist for electroless plating, a layer of the composition and a support for supporting the layer. The present invention relates to a method for producing a photosensitive element including a body film and a plating resist.

[0002]

2. Description of the Related Art Conventionally, a printed wiring board is manufactured mainly by a subtractive method in which a through-hole conductive portion is formed by using both electroless thinning plating and electrolytic plating, and a wiring pattern portion is formed by etching. ing. On the other hand, an additive method of forming a through-hole conductive portion and a wiring pattern portion by electroless plating has been put into practical use, and is suitable for fine wiring and a small-diameter through-hole, and is therefore attracting attention as a future high-density printed wiring board manufacturing method.

In this additive method, high alkalinity (usually pH 11 to 13.5) and high temperature (usually 60 to 1) are used.
A resist for electroless plating that withstands an electroless plating solution at 80 ° C. for a long time (usually 4 to 50 hours) is required, and usually, in order to form fine wiring of 150 μm (line width and interval), a screen is used. Printing resists are difficult and photoresists are applied.

Proposals for photoresists for the additive method are disclosed in Japanese Patent Laid-Open Nos. 50-43468 and 54-77.
0, JP-A-58-100490, JP-A-5
No. 8-199341, JP-A-59-12434, JP-A-60-101532, and the like. Further, Japanese Patent Laid-Open No. 63-18692 discloses a photoresist which is less prone to contamination by an electroless copper plating solution and is excellent in mass productivity. However, these proposed photoresists all use an organic solvent such as 1,1,1-trichloroethane as a developing solution, and thus have problems in working environment and processing cost. Further, due to recent problems of environmental pollution, the use of halogen-based organic solvents has been regulated, and there has been a demand for photoresists that can be developed with an alkaline aqueous solution even in the additive method.

As an alkali developing type photoresist,
JP-A-62-158710, JP-A-62-285
In Japanese Patent Laid-Open No. 903 and Japanese Patent Laid-Open No. 63-11930,
Disclosed is a resin composition comprising a copolymer of maleic anhydride and an unsaturated hydrocarbon compound or a copolymer of maleic anhydride and styrene with a ring-opening addition of hydroxyalkylene (meth) acrylate as a base polymer. The plating resist formed by using this resin composition has a problem that in the electroless copper plating step, a part of the plating resist is peeled off with time or the plating solution is contaminated and the copper deposition rate is reduced. It was

As a photoresist for electroless copper plating which can be developed with an aqueous alkaline solution, JP-A-2-166452 is known.
In the publication, hydroxyalkylene (meth) is added to a copolymer of maleic anhydride and an aromatic hydrocarbon having a vinyl group.
Disclosed is an alkali-developing resin composition containing a compound to which an acrylate is added and a carboxyl group-containing epoxy acrylate. The plating resist formed using this resin composition has a low flexibility and thus cracks occur during electroless copper plating, and when used as a photosensitive element, when it is cut with a cutter or the like, the photosensitive material around the cut portion is exposed. Layers may scatter (scattered debris may attach to undesired locations and cause defects), or
There is a problem that the plating solution is contaminated and the copper deposition rate decreases.

As a photoresist which can be developed with an alkaline aqueous solution and has resistance to an alkaline etchant,
Japanese Unexamined Patent Publication (Kokai) No. 62-153308 discloses a photopolymerizable curable resin composition using a polymer having a side chain of polyethylene glycol whose terminal group is a phenoxy group.
The plating resist formed using this resin composition is subjected to an alkali etching step (for example, pH 8 to 9 and temperature 5
It exhibits relatively good resistance at 0 ° C. for 1 to 3 minutes), but in the electroless copper plating step, a part of the plating resist is peeled off or the plating solution is contaminated and the copper deposition rate decreases with time. There was a problem.

Japanese Unexamined Patent Publication No. 2-230154 discloses a compound obtained by adding glycidyl methacrylate to a binary copolymer of styrene and mono-iso-propyl maleate as a copper plating resist material that can be developed with an alkaline aqueous solution. And a polymer typified by a terpolymer of benzyl methacrylate, 2-hydroxybutyl methacrylate and methacrylic acid are also disclosed. The plating resist formed by using this resin composition exhibits relatively good substrate adhesion, but in the electroless copper plating process, there is a problem that part of the plating resist peels off.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems of the prior art, and has good developability with an alkaline aqueous solution, photosensitivity, resolution,
Photosensitive properties suitable as a photoresist for electroless copper plating with excellent plating resistance, no abnormal deposition of plated copper and contamination of plating solution, and excellent electrical insulation and electrolytic corrosion resistance when used as a permanent resist. Provided is a resin composition, a photosensitive element having a layer of the composition and a support film supporting the layer, and a method for producing a plating resist.

[0010]

The present invention provides (A) (a) a vinyl monomer represented by the general formula (I) 1
0 to 90 parts by weight

[Chemical 3] (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an amino group or a carboxyl group. A group selected from the group consisting of: (b) maleic anhydride 10 to 90 parts by weight;
And a polymer compound obtained by copolymerizing the component (b) in an amount of 100 parts by weight in total, (c) the following general formula (I
Compounds represented by I)

[Chemical 4] (Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, and R ₈ represents an alkylene group having 1 to ₈ carbon atoms or a benzene ring), hydroxyl equivalent / acid anhydride Unsaturated polymer compound obtained by reacting at an equivalence ratio of 0.1 to 1.2, (B) a photopolymerizable unsaturated compound having at least two ethylene groups at the end, and (C) irradiation with active light A photosensitive resin composition containing a photoinitiator that generates free radicals, a photosensitive element having a layer of the photosensitive resin composition and a support film supporting the layer, and the photosensitive resin composition. The solution is applied onto a substrate, dried, imagewise exposed and then developed, and a method for producing a plating resist, and a layer of the photosensitive resin composition of the photosensitive element is laminated on the substrate to form an image. Exposure and then development Preparative process for producing a plating resist according to claim.

The photosensitive resin composition of the present invention will be described in detail below. The photosensitive resin composition of the present invention contains the above unsaturated polymer compound as an essential component [component (A)]. Such an unsaturated polymer compound can be easily produced by reacting the polymer compound obtained by copolymerizing the components (a) and (b) with the component (c). In the vinyl monomer represented by the general formula (I) as the component (a), R ₁ represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, and R ₂ , R ₃ and R ₄ are each independently Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an amino group or a carboxyl group, and a hydrogen atom and a hydroxyl group are preferable. Examples of the vinyl monomer represented by the general formula (I) as the component (a) include styrene, α-methylstyrene, p-vinylphenol and p.
-Vinyltoluene, p-vinylaniline, p-vinylbenzoic acid and the like can be mentioned, with styrene and p-vinylphenol being preferred. The component (b) is maleic anhydride. Other acid anhydrides have poor copolymerizability.

In the unsaturated polymer compound of the component (A) used in the present invention, the sum of the components (a) and (b) is 1
It is obtained by blending so as to be 00 parts by weight and copolymerizing. The amount of the component (a) used is 10 to 90 parts by weight, preferably 30 to 70 parts by weight. (A)
If the amount of the component used is less than 10 parts by weight, the electroless copper plating resistance is deteriorated. On the other hand, if it exceeds 90 parts by weight, the alkali developability is deteriorated. The amount of the component (b) used is 10 to 90 parts by weight, preferably 30 to 70 parts by weight. When the amount of the component (b) used is less than 10 parts by weight, the alkali developability deteriorates, and when it exceeds 90 parts by weight, the electroless copper plating resistance deteriorates.

Next, in the compound represented by the general formula (II) as the component (c), R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group. R ₈ has 1 to 1 carbon atoms
It is difficult to obtain those having an alkylene group of 8 or a benzene ring and having more than 8 carbon atoms. The compound represented by the general formula (II) as the component (c) has the following general formula (III)

[Chemical 5] (Wherein R ₅ , R ₆ and R ₈ have the same meanings as in formula (II)), and a carboxyl group-containing vinyl monomer represented by the following formula (IV)

[Chemical 6] It is obtained by reacting with an oxirane ring-containing vinyl monomer represented by the formula (R ₇ has the same meaning as in formula (II)). Examples of the compound represented by the general formula (III) include β- (meth) acryloyloxyethyl hydrogen succinate and β- (meth) acryloyloxyethyl hydrogen phthalate. The compound represented by the general formula (III) is commercially available from Shin Nakamura Chemical Co., Ltd. Examples of the compound represented by the general formula (IV) include glycidyl (meth) acrylate.

By reacting the compound represented by the general formula (III) with the compound represented by the general formula (IV), the component (c) is obtained. For example, the compound represented by the general formula (III) and the compound represented by the general formula (IV) are dissolved in an inert organic solvent such as a ketone solvent, a cellosolve acetate solvent, an ether solvent, a nonpolar solvent, A tertiary amine such as triethylamine, tri-n-butylamine, diethylcyclohexylamine and triethylenediamine, a catalyst such as quaternary ammonium salt such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride is added, and a polymerization inhibitor such as hydroquinone and p- Add methoxyphenol etc.,
The component (c) can be obtained by reacting these compounds at 65 to 115 ° C. in the presence of oxygen.

By reacting these compounds [component (c)] with the polymer compound of the preceding period, the unsaturated polymer compound of component (A) can be obtained. For example, the polymer compound is dissolved in an inert organic solvent such as a ketone-based solvent, a cellosolve acetate-based solvent, an ether-based solvent, or a nonpolar solvent, and triethylamine, tri-n-butylamine, diethylcyclohexylamine, triethylenediamine or the like is added. Catalysts such as quaternary ammonium salts such as primary amines, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, etc., and hydroquinone, p-methoxyphenol, etc. as polymerization inhibitors are added to these compounds in the presence of oxygen. By reacting at 65 to 115 ° C, the unsaturated polymer compound as the component (A) can be obtained.

Here, the polymer compound and the component (c) are
The reaction is carried out with the hydroxyl equivalent / acid anhydride equivalent ratio being in the range of 0.1 to 1.2. If the equivalent ratio is less than 0.1, the electroless copper plating resistance is deteriorated. If the equivalent ratio exceeds 1.2, gelation occurs during production or the alkali developability is deteriorated.

The amount of the component (A) obtained as described above is preferably 20 to 90 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B), and 30
It is more preferable that the amount is -80 parts by weight. When the amount of the component (A) used is too small, edge fusion tends to occur due to the flow of the photosensitive layer in the case of a photosensitive element. Also, if the component (A) is too much. The sensitivity and resistance to electroless copper plating tend to decrease.

As the photopolymerizable unsaturated compound having at least two terminal ethylene groups, which is the component (B) used in the present invention, those conventionally known as photopolymerizable polyfunctional monomers can be used. . For example, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, Trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (the number of propylene groups is 2 to 2).
14), dipentaerythritol penta (meta)
Acrylate, dipentaerythritol hexa (meth)
Bisphenol A, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol such as acrylate
Dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate and other bisphenol A polyoxyethylene di (meth) acrylate, trimethylolpropane triglycidyl ether Compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl group-containing compounds such as triacrylate and bisphenol A diglycidyl ether diacrylate, polyvalent carboxylic acids (phthalic anhydride, etc.), hydroxyl groups and ethylenically unsaturated compounds An esterification product with a substance having a group (β-hydroxyethyl (meth) acrylate, etc.), (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester,
(Meth) acrylic acid 2-ethylhexyl ester and other alkyl esters of acrylic acid or methacrylic acid, reaction products of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylic acid ester, trimethylhexamethylene diisocyanate, cyclohexanedimethanol and 2- Examples thereof include urethane (meth) acrylates such as reaction products with hydroxyethyl (meth) acrylic acid ester, and among these, bisphenol A polyoxyethylene dimethacrylate is preferable.

As the photopolymerizable unsaturated compound as the component (B), an acid anhydride-modified epoxy acrylate may be used, and examples of the acid anhydride-modified epoxy acrylate include orthocresol novolac type epoxy resin and phenol. At least one kind of novolak type epoxy resin selected from the group consisting of novolac type epoxy resin and halogenated phenol novolac type epoxy resin and an unsaturated carboxylic acid are used in a carboxyl group equivalent / epoxy group equivalent ratio of 0.5 to 1.05. In the range, a compound obtained by reacting an unsaturated compound obtained by addition reaction with a saturated or unsaturated polybasic acid anhydride can be mentioned. When these acid anhydride-modified epoxy acrylates are used as the photopolymerizable unsaturated compound, particularly good electroless copper plating resistance is exhibited. These compounds as the component (B) can be used alone or in combination of two or more kinds.

The amount of the component (B) used is preferably 10 to 80 parts by weight, and more preferably 20 to 70 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). , And more preferable. When the amount of the component (B) used is too small, the sensitivity and the resistance to electroless copper plating tend to decrease,
If it is too large, the viscosity of the photosensitive resin composition is lowered, and edge fusion tends to occur.

Examples of the (C) component photoinitiator used in the present invention include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), and N, N'-tetraethyl-4. , 4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone and other aromatic ketones, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ethers, benzyldimethylketone Benzyl ketal such as tar and benzyl diethyl ketal, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl)-
4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)
-4,5-diphenylimidazole dimer, 2-di (p
-Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-
Phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-
2,4,5-triarylimidazole dimers such as diphenylimidazole dimers and the like can be mentioned. These can be used alone or in combination of two or more, and the amount thereof is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and 0 More preferably, it is from 0.05 to 10 parts by weight.
If the amount used is too small, sufficient photosensitivity tends not to be obtained, and if the amount is too large, light absorption on the surface of the composition increases during exposure, and internal photocuring tends to be insufficient. There is.

The photosensitive resin composition of the present invention may further contain other auxiliary components. The secondary components include thermal polymerization inhibitors, dyes, pigments, coatability improvers and the like, and these are selected under the same consideration as for ordinary photosensitive resin compositions. It is possible to contain a small amount of an epoxy resin as a secondary component within a range that does not impair the object of the present invention.

Next, the photosensitive element of the present invention will be described in detail below. The photosensitive element proposed by the present invention can be obtained by forming a layer of the above-mentioned photosensitive resin composition on a support film. The formation of the layer of the photosensitive resin composition on the support film can be carried out by a conventional method. For example, the photosensitive resin composition is uniformly dissolved in an organic solvent such as methyl ethyl ketone, toluene and methylene chloride,
This solution is applied onto the support film by a knife coating method, a roll coating method or the like, and dried. The amount of residual solvent in the photosensitive layer is preferably 2% by weight or less in order to maintain the characteristics.

The support film used in the present invention preferably has the heat resistance and solvent resistance necessary for producing the photosensitive element. A release film such as Teflon film or release paper is used as a temporary support film, a layer of the photosensitive resin composition is formed thereon, and then a film having low heat resistance or solvent resistance is formed on this layer. It is also possible to laminate and peel off the temporary support film to produce a photosensitive element having a support film having low heat resistance or solvent resistance. The support film may be transparent or opaque to actinic light. Examples of support film that can be used, polyester film, polyimide film, polyamide-imide film,
Known films such as polypropylene film and polystyrene film can be mentioned.

In the case of producing a long photosensitive element, the element is wound into a roll at the final stage of production. In this case, by using a known method with a pressure-sensitive adhesive tape or the like, by using a backside treated support film,
It is possible to prevent the transfer of the layer of the photosensitive resin composition to the back surface of the support film when wound in a roll. For the same purpose, the purpose of preventing the adhesion of dust, etc., it is preferable to laminate a peelable cover film on the layer of the photosensitive resin composition of the element.

Examples of peelable cover films include:
There are polyethylene film, polypropylene film, Teflon film, surface-treated paper, etc., and the layer of the photosensitive resin composition is more important than the adhesive force between the layer of the photosensitive resin composition and the support film when the cover film is peeled off. The adhesive force between the cover film and the cover film may be smaller.

The thickness of the layer of the photosensitive resin composition constituting the photosensitive element of the present invention varies depending on the thickness of plated copper deposited by electroless plating, but is usually 10 to 100.
μm.

The photosensitive resin composition of the present invention is applied as a solution to a substrate, and after drying, or as a photosensitive element, a layer of the photosensitive resin composition is laminated on the substrate, exposed imagewise, and then developed. Then, a plating resist is manufactured.

Next, an example of how to use the photosensitive element of the present invention will be described. Lamination of the photosensitive element proposed by the present invention on a substrate is easy. That is, if there is no cover film, as it is, if there is a cover film peeling the cover film or while peeling,
The photosensitive resin composition layer is heated and pressure-laminated on the substrate side. The heating and pressure laminating can be performed using a normal pressure laminator well known to the printed wiring board manufacturers. When the substrate has an unevenness of 10 μm or more, such as a printed wiring board on which conductor wiring lines are formed, it is preferable to stack under reduced pressure or under vacuum. As a device for this purpose, Japanese Patent Publication Sho 5
There is a stacking device described in JP-A-3-31670 or JP-B-55-13341.

In the additive method, an insulating substrate is usually used as the substrate. As the insulating substrate, a laminated plate of paper phenol, glass epoxy or the like, an iron enamel substrate, a substrate with a metal core such as a substrate having an epoxy resin insulating layer formed on both sides of an aluminum plate and the like can be used. It is also possible to immerse these substrates in a solution containing a plating catalyst after drilling, and attach the plating catalyst to the inner wall of the through hole. As such a plating catalyst solution, a sensitizer HS manufactured by Hitachi Chemical Co., Ltd.
-101B etc. can be used. An adhesive layer is preferably applied to the surface of the substrate in order to improve the adhesion of the plating catalyst or to improve the adhesion of the deposited electroless plated copper to the substrate.

As the adhesive, one known as an adhesive for additive method such as a phenol-modified nitrile rubber adhesive can be used. Epoxy resins, epoxy-modified polyimide resins, polyimide resins disclosed in JP-A-61-276875, which are excellent in electrolytic corrosion resistance and heat resistance,
It is preferable to use an adhesive agent in which fine powder of a cured heat-resistant resin such as an epoxy resin, a polyester resin or a bismaleimide-triazine resin is dispersed in an uncured heat-resistant resin such as a phenol resin. There is also a method of ensuring adhesion of the plated copper to the substrate by forming fine irregularities on the surface of the substrate itself, and in this case, an adhesive layer is not particularly required.

A laminated plate in which a compound such as a Pd compound which serves as a catalyst for electroless copper plating is dispersed is a preferable substrate when electroless plated copper is deposited on the inner wall of the through hole. As a substrate having an adhesive layer containing a plating catalyst formed on the surface of a glass epoxy laminated plate containing a plating catalyst inside, there is a laminated plate ACL-E-161 manufactured by Hitachi Chemical Co., Ltd. When such a substrate is used, the step of newly attaching the plating catalyst becomes unnecessary. In order to improve the adhesion of the plating catalyst or the adhesion of the deposited electroless plated copper, it is preferable to roughen the adhesive layer surface before the electroless plating treatment. As a roughening method, there is a method of immersing in an acidic solution containing sodium dichromate or chromic acid, etc., but as is known, if the roughening step is before the electroless copper plating step, the photosensitive element is laminated. It does not matter whether before or after forming the plating resist pattern.

The exposure and development treatment after lamination can be carried out by a conventional method. That is, when the support film is opaque to actinic light, the support film is peeled off and imagewise exposed through a negative mask using a light source such as a high pressure mercury lamp or an ultrahigh pressure mercury lamp. Heat treatment at 50 ° C. to 100 ° C. before and after exposure is preferable in order to enhance the adhesion between the substrate and the photosensitive resin layer.

Examples of the developing solution used in the developing treatment include alkaline aqueous solutions such as an aqueous solution of an alkali metal hydroxide, an aqueous solution of an alkali metal phosphate and an aqueous solution of an alkali metal carbonate such as sodium carbonate. Of these, an aqueous solution of sodium carbonate is preferable.

The alkali development of the resin composition of the present invention can be carried out at a developer temperature of 10 to 50 ° C., preferably 20 to 40 ° C., using a commercially available developing machine.

After forming the plating resist pattern in this manner, it is preferable to re-irradiate with active light using a light source such as a high pressure mercury lamp or an ultrahigh pressure mercury lamp from the viewpoint of improving the chemical resistance of the plating resist. Furthermore, it is preferable to perform heat treatment after re-irradiation with active light from the viewpoint of improving electroless plating resistance. As the heating temperature and the heating time, for example,
140-160 degreeC and 40-90 minutes are mentioned, respectively.

A solution of the photosensitive resin composition proposed by the present invention is directly applied to a substrate by a dip coating method, a flow coating method or the like, and after drying with a solvent, a film which is transparent to active light such as a polyester film or the like is directly applied. After lamination, similarly as in the case of the photosensitive element in the previous period, imagewise exposure through a negative mask, development, and more preferably exposure to actinic light also form a plating resist having excellent characteristics as described above. it can.

[0038]

EXAMPLES The present invention will now be described in detail with reference to examples. In addition, "part" in an Example and a comparative example shows a weight part.

Synthesis Example 1 Synthesis of unsaturated compound (a-1) A. β-acryloyloxyethyl hydrogen succinate 184.8 parts Benzyltrimethylammonium chloride 0.36 part Hydroquinone 0.1 part Propylene glycol monomethyl ether acetate (solvent) 257 parts B.I. Glycidyl methacrylate 121.6 parts Propylene glycol monomethyl ether acetate (solvent) 50 parts Reactor of the above A equipped with a thermometer, a stirrer, a cooling pipe, a dry air introduction pipe and a dropper, capable of heating and cooling and having a volume of about 1 liter. In addition, the temperature was raised to 115 ° C., and B was added dropwise uniformly over 0.5 hour. After dropwise addition of B, stirring was continued at 115 ° C. for about 20 hours and then cooled to room temperature to obtain unsaturated compound (a-1).
Got The epoxy group equivalent / carboxyl group equivalent ratio is 1.0.

Synthesis Example 2 Synthesis of unsaturated compound (a-2) In Synthesis Example 1, the components of A and B were changed to those shown below. A. β-acryloyloxyethylhydrodienephthalate 226 parts Benzyltrimethylammonium chloride 0.36 parts Hydroquinone 0.1 parts Propylene glycol monomethyl ether acetate (solvent) 257 parts B.I. Glycidyl methacrylate 121.6 parts Propylene glycol monomethyl ether acetate (solvent) 50 parts By using the above A and B in the same manner as in Synthesis Example 1, an unsaturated compound (a-2) was obtained. The epoxy group equivalent / carboxyl group equivalent ratio is 1.0.

Synthesis Example 3 Synthesis of unsaturated polymer compound (A-1) A. Styrene / maleic anhydride copolymer (RPC-1022 manufactured by Nippon Monsanto Co., Ltd.) 100 parts Dioxane (solvent) 356 parts B.I. Unsaturated compound (a-1) synthesized in Synthesis Example 1 (solid content) 141.7 parts Triethylenediamine 0.11 part Hydroquinone 0.1 part Propylene glycol monomethyl ether acetate (solvent) 208 parts The above A is a thermometer and stirred. The reactor was equipped with a device, a cooling pipe, a dry air introduction pipe, and a dropping device and had a volume of about 2 l capable of heating and cooling. The temperature was raised to 100 ° C., and B was uniformly added dropwise over 0.5 hour. After the dropwise addition of B, the mixture was continuously stirred at 100 ° C. for about 20 hours and then cooled to room temperature to obtain an unsaturated polymer compound
-1) was obtained. The hydroxyl equivalent / acid anhydride equivalent ratio is 0.8.

Synthesis Example 4 Synthesis of unsaturated polymer compound (A-2) A. Styrene / maleic anhydride copolymer (RPC-1022 manufactured by Nippon Monsanto Co., Ltd.) 100 parts Dioxane (solvent) 356 parts B.I. Unsaturated compound (a-2) synthesized in Synthesis Example 2 (solid content) 160.7 parts Triethylenediamine 0.11 part Hydroquinone 0.1 part Propylene glycol monomethyl ether acetate (solvent) 253 parts Using A and B above The unsaturated polymer compound (A-2) was obtained by the same procedure as in Synthesis Example 1. In addition,
The hydroxyl equivalent / acid anhydride equivalent ratio is 0.8.

Comparative Synthesis Example 1 In Synthesis Example 1, the components of A and B were changed to those shown below. A. Styrene / maleic anhydride copolymer (RPC-1022 manufactured by Nippon Monsanto Co., Ltd.) 100 parts Dioxane (solvent) 356 parts B.I. Hydroxyethyl acrylate 45.9 parts Triethylenediamine 0.11 parts Hydroquinone 0.1 parts Propylene glycol monomethyl ether acetate (solvent) 92 parts By using the above A and B in the same manner as in Synthesis Example 1, high unsaturation is obtained. A molecular compound (A-3) was obtained. In addition,
The hydroxyl equivalent / acid anhydride equivalent ratio is 0.8.

Synthesis Example 5 Synthesis of Acid Anhydride Modified Epoxy Acrylate Resin A. Phenol novolac type epoxy resin (EPPN-201 manufactured by Nippon Kayaku Co., Ltd.) 741 parts Propylene glycol monomethyl ether acetate 800 parts B.I. Acrylic acid 298 parts Parabenzoquinone 1.7 parts Benzyltrimethylammonium chloride chloride 1.25 parts C.I. Tetrahydrophthalic anhydride 234 parts The above A was added to a reactor having a thermometer, a stirrer, a cooling pipe, a dry air introduction pipe and a dropper, which can be heated and cooled and has a volume of about 5 liters, and the temperature was raised to 115 ° C. , Reaction temperature 11
While maintaining at 0 to 120 ° C, B evenly over 0.5 hours
Was dripped. After the dropwise addition of B, stirring was continued at 115 ° C. for about 20 hours to reduce the acid value of the reaction system to 13 or less, then cooled to 65 ° C., and C was added. After the addition of C, the reaction system was kept at 65 ° C. and stirring was continued for about 6 hours to adjust the acid value of the reaction system to 75 to obtain an acid anhydride-modified epoxy acrylate resin. The epoxy group equivalent / carboxyl group equivalent ratio is 1.0.

Examples 1-3, Comparative Examples 1-2 Component (A) obtained in Synthetic Examples 3-5 and Comparative Synthetic Example 1,
And (B) component, (C) component, dye and organic solvent,
Mixing ratios shown below and in Table 1 (parts by weight)
To obtain a solution of the photosensitive resin composition.

[0046]

[Table 1]

Next, using the apparatus shown in FIG. 1, the solution 6 of the photosensitive resin composition having the above composition was uniformly applied onto the polyethylene terephthalate film 12 having a thickness of 25 μm, and 8
It was dried by a hot air convection dryer 7 at 0 to 100 ° C. for about 10 minutes. The thickness of the photosensitive resin composition layer after drying is about 35 μm.
It was m. On the layer of the photosensitive resin composition, a polyethylene film 13 having a thickness of about 25 μm was attached as a cover film as shown in FIG. 1 to obtain a photosensitive element. In FIG. 1, reference numeral 1 is a polyethylene terephthalate film feeding roll, 2, 3 and 4 are rolls, 5 is a knife, 8 is a polyethylene film feeding roll, 9 and 10 are rolls and 11 is a photosensitive element winding roll.

The resulting photosensitive element was tested for developability with respect to an aqueous alkaline solution, exposure sensitivity, splattering property, storage stability, and electroless copper plating resistance after resist formation by the following methods. The results are shown in Table 1.

(1) Developability with Alkaline Aqueous Solution Hitachi Chemical Co., Ltd. Additive Process Substrate ACL-E-1
68 (a substrate in which a phenol-modified nitrile rubber adhesive containing a plating catalyst is applied to both sides of a glass epoxy laminate containing a Pd-based plating catalyst to a thickness of about 30 μm) is polished with Sumitomo 3M Scotch Bright and washed with water. Then 8
It was dried at 0 ° C. for 15 minutes. The photosensitive element obtained above was laminated on both sides of this test substrate by using a A-500 type laminator manufactured by Akebono Sangyo Co., Ltd. while peeling off the polyethylene cover film. Next, after peeling off the polyethylene terephthalate film, spray development was performed for 70 seconds at 30 ° C. using a 1 wt% sodium carbonate aqueous solution. After development, 3
The alkali developability was visually evaluated for the resin remaining after being magnified 0 times. The evaluation criteria are as follows. ◯: Good developability (no resin left on the substrate surface) X: Poor developability (some resin left on the substrate surface)

(2) Exposure sensitivity After stacking the photosensitive element on the test substrate in the same manner as in (1), Kodak Step Tablet No. 2 (Eastman Kodak Company, 21-step step tablet) was adhered to the photosensitive layer from the top of the polyethylene terephthalate film, using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. to obtain 7 step tablet steps. The required exposure dose (mJ / cm ² ) was determined.

(3) Storage stability A 90 m long photosensitive element wound into a roll was stored at a temperature of 23 ° C. and a humidity of 60%, and the state of the exudation of the photosensitive layer from the side surface of the roll was maintained for 6 months. It was evaluated visually. The evaluation criteria are as follows. ◯: Good storage stability (no bleeding of the photosensitive layer even after 6 months) X: Poor storage stability (those where bleeding of the photosensitive layer occurred within 6 months)

(4) Electroless Copper Plating Resistance The above-mentioned additive method substrate ACL- manufactured by Hitachi Chemical Co., Ltd.
A test board in which through holes with a diameter of 0.8 mm were drilled at 2.54 mm intervals with an NC drill in E-168 was polished with Scotch Bright manufactured by Sumitomo 3M, washed with water, and then at 80 ° C. for 1 hour.
It was dried by heating for 5 minutes. The obtained photosensitive elements were laminated on both sides of this test substrate while peeling off the polyethylene cover film using an A-500 type laminator manufactured by Akebono Sangyo Co., Ltd., and then a test negative mask shown in FIG. 2 was adhered from above the polyethylene terephthalate film. Then, exposure was carried out using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. so as to obtain 7 step tablet stages. After the exposure, the negative mask was peeled off, and then heated at 80 ° C. for 5 minutes. Reference numeral 14 indicates an opaque portion of the negative mask, and 15 indicates a transparent portion of the negative mask. Then, using a 1 wt% sodium carbonate aqueous solution, 30
Spray development was carried out at 70 ° C. for 70 seconds. After development, 10 at 80 ℃
After heating and drying for 1 minute, ultraviolet rays were re-irradiated at a dose of ³ J / cm ² using an ultraviolet ray irradiation device manufactured by Toshiba Denshi. Furthermore, 15
Heated at 0 ° C. for 1 hour. The test substrate thus formed with the resist image was prepared by dissolving 20 g of sodium dichromate in 1 liter of a 42% aqueous solution of borofluoric acid at 40 ° C.
It was dipped in the solution for 15 minutes to roughen the exposed part of the adhesive layer, washed with water, then dipped in hydrochloric acid having a concentration of 3 N for 5 minutes, and washed with water. This test substrate contains 15 g / l of CuSO ₄ .5H ₂ O, 30 g / l of ethylenediaminetetraacetic acid, 10 ml / l of 37% HCHO aqueous solution and 25 mg / l of sodium cyanide, and is electroless copper adjusted to pH 12.5 with sodium hydroxide. Immerse in plating solution at 72 ℃ for 24 hours, wash with water, and then at 80 ℃
And dried for 10 minutes. After performing such an operation, the resist image is magnified 30 times, and the resist crack evaluation criteria are as follows. ◯: Good resistance to electroless copper plating (no cracking, floating, or peeling of the resist) △: Slightly poor resistance to electroless copper plating (floating on a part of the resist or peeling) X): Poor resistance to electroless copper plating (cracks, floats, and peeling on the entire resist surface)

(5) Contamination of Plating Solution By measuring the copper thickness of the copper pattern formed by electroless copper plating, the influence of the contamination of the plating solution on the deposition rate of copper was investigated.

(6) Scattering property After the photosensitive element was stored at a temperature of 23 ° C. and a humidity of 60% for 24 hours, the polyethylene cover film was peeled off and cut at a constant speed with a cutter knife to scatter the photosensitive layer at the cut portion. Was visually evaluated. The evaluation criteria are as follows. ◯: Good splattering property (no photosensitive layer chipping) Δ: Slightly splattering property (somewhat photosensitive layer chipping) X: Poor splattering property (photosensitive layer chipping) Is marked)

[0055]

[Table 2] (Note) Both the components (A) and (B) are the solid content.

[0056]

EFFECT OF THE INVENTION The photosensitive resin composition of the present invention and the photosensitive element using the same exhibit excellent alkali developability and excellent resolution, and the plating resist formed by them has abnormal deposition of plated copper. It is suitable as a plating resist for electroless copper plating because it does not contaminate the plating solution or has excellent plating resistance. Further, since the photosensitive element according to the present invention does not scatter at the time of cutting, it has excellent workability and can improve the yield of printed wiring boards and the like. Further, since the photosensitive resin composition of the present invention and the photosensitive element using the same exhibit good chemical resistance, they can be suitably used as etching resists and electroplating resists.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus for manufacturing a photosensitive element used in Examples and Comparative Examples.

FIG. 2 is a diagram showing test negative masks used in Examples and Comparative Examples.

[Explanation of symbols]

1 ... Polyethylene terephthalate film feeding roll 2, 3, 4 ... Roll 5 ... Knife 6 ... Solution of photosensitive resin composition 7 ... Dryer 8 ... Polyethylene film feeding roll 9, 10 ... Roll 11 ... Photosensitive element winding roll 12 ... polyethylene terephthalate film 13 ... polyethylene film 14 ... opaque part of negative mask 15 ... transparent part of negative mask

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsuyoshi Nojiri 4-13-1, Higashimachi, Hitachi-shi, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Institute

Claims (6)

[Claims] 1. A vinyl monomer represented by the general formula (I) (A) (a) in an amount of 10 to 90 parts by weight: (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an amino group or a carboxyl group. A group selected from the group consisting of: (b) maleic anhydride 10 to 90 parts by weight;
And a polymer compound obtained by copolymerizing the component (b) in an amount of 100 parts by weight in total, (c) the following general formula (I
A compound represented by I): (Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, and R ₈ represents an alkylene group having 1 to ₈ carbon atoms or a benzene ring), hydroxyl equivalent / acid anhydride An unsaturated polymer compound obtained by reacting with an equivalent ratio in the range of 0.1 to 1.2, (B) a photopolymerizable unsaturated compound containing at least two ethylene groups at the end, and (C) active light A photosensitive resin composition containing a photoinitiator that generates free radicals upon irradiation with. 2. An unsaturated polymer compound (A) 20 to 90.
Parts by weight, (B) 10-80 parts by weight of a photopolymerizable unsaturated compound containing at least two ethylene groups at the end ((A)
+ (B) = 100 parts by weight) and (C) 0.01 to 20 parts by weight of a photoinitiator that generates free radicals by irradiation with active light ((A) + (B) = 100 parts by weight). The photosensitive resin composition according to claim 1, which contains. 3. A photosensitive element having a layer of the photosensitive resin composition according to claim 1 and a support film supporting the layer. 4. The photosensitive element according to claim 3, further comprising a peelable cover film laminated on the layer of the photosensitive resin composition. 5. A method for producing a plating resist, which comprises applying a solution of the photosensitive resin composition according to claim 1 or 2 onto a substrate, drying, imagewise exposing and then developing. 6. A method for producing a plating resist, which comprises laminating a layer of the photosensitive resin composition of the photosensitive element according to claim 3 or 4 on a substrate, imagewise exposing and then developing.