JP2000147765A - Photosensitive resin composition, photosensitive element and production of resist using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. suitable as a photoresist for electroless copper plating having excellent heat resistance for soldering, electric insulating property and resistance against electrochemical corrosion by incorporating a specified carboxyl group-contg. polyhydroxyether resin compd., a photopolymerizable unsatd. compd. having at least one ethylenic unsatd. group at the molecular end, a photopolymn. initiator and a specified compd. SOLUTION: This compsn. consists of a specified carboxyl group-contg. polyhydroxyether resin compd. produced by reacting carboxyl groups with hydroxyl groups in a polyhydroxyether resin having a repeating unit expressed by the formula, a photopolymerizable unsatd. compd. having at least one ethylenic unsatd. group at the molecular end, a photopolymn. initiator which produces free radicals by active rays, and a specified compd. The photopolymn. initiator contains at least one kind selected from 2,4,5-triarylimidazole dimers. In the formula, R1 is a bivalent satd. aliphatic hydrocarbon group, each of R2 and R3 is independently 1-4C alkyl group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element, and a method for producing a plating resist using the same.

[0002]

2. Description of the Related Art A printed wiring board is mainly manufactured by a subtractive method in which a through-hole conductive portion is formed by using both electroless thin plating and electrolytic plating, and a wiring pattern portion is formed by etching. I have. 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 to practical use. In the additive method, fine wiring equivalent to the resolution of the resist can be formed because the copper is deposited by plating the copper along the walls of the plating resist by electroless plating. Therefore, it is attracting attention as a method for manufacturing a high-density printed wiring board.

In the additive method, a high alkali (usually pH = 11 to 13.5) and a high temperature (usually 60 to 13.5) are used.
A resist for electroless electroplating that can withstand an electroless plating solution of 80 ° C) for a long time (typically 4 to 50 hours) is required.
In addition, it is difficult to form fine wiring having a width of 150 μm (line width and interval) with a screen printing resist.
Photoresist is required.

A photoresist for an additive method has been proposed in Japanese Patent Application Laid-Open Nos. 50-43468 and 54-77.
0, JP-A-58-100490, JP-A-5100
This is described in JP-A-8-199341, JP-A-59-12434, JP-A-60-101532 and the like. Further, a photoresist which is less contaminated by an electroless copper plating solution and has excellent mass productivity is disclosed in Japanese Patent Application Laid-Open No. 62-18692. However, these proposed photoresists all use an organic solvent such as 1,1,1-trichloroethane, and have problems in terms of working environment and processing cost. Furthermore, the use of halogen-based organic solvents is regulated due to the problem of environmental pollution, and the working environment is good even with the additive method and there is no problem of environmental pollution, that is, a photoresist using a developing solution that does not use a halogen-based organic solvent is used. There is a need for a method of manufacturing a printed wiring board.

As a photoresist for electroless plating which can be developed with an aqueous alkali solution, JP-A-2-166452 discloses a copolymer of maleic anhydride and an aromatic hydrocarbon having a vinyl group with hydroxy (meth) acrylate. And a resin composition of an alkali development type represented by a resin composition containing a compound added with a carboxy group-containing epoxy acrylate.

Japanese Unexamined Patent Publication (Kokai) No. 2-230154 discloses styrene and mono-iso-propyl maleate as copper plating resist materials which can be developed with an aqueous alkali solution.
It contains both a polymer represented by a compound obtained by adding glycidyl methacrylate to a copolymer and a polymer represented by a terpolymer of benzyl methacrylate, 2-hydroxybutyl methacrylate and methacrylic acid. A photopolymerizable composition is disclosed.

JP-A-5-72735 discloses a photoresist for electroless plating which can be developed with an aqueous alkali solution, which is dissolved or swelled in an aqueous alkali solution with a graft polymer having a polymer of a monomer having a hydrophilic group as a branch polymer. A photosensitive resin composition containing a binder polymer is disclosed.

Japanese Patent Application Laid-Open No. 5-107760 discloses a photoresist for electroless plating which can be developed with an alkaline aqueous solution, a binder polymer which dissolves or swells in an alkaline aqueous solution, and a compound which generates a strong acid upon irradiation with active energy rays. A photosensitive resin composition containing a methylol (meth) acrylamide derivative copolymer is disclosed.

However, these proposed photoresists have problems such as low tolerance of electroless copper plating resistance, high pH of a plating solution, and blistering or peeling of the resist when the plating time is long. It is difficult to use in practical processes. Further, since a large amount of carboxylic acid remains in these resists, the pH is 12 to 13.
The resist swells in the plating solution. When the resist is dried and shrunk in the drying step after the plating copper is deposited in this state, there is an essential problem that a gap is generated between the resist and the plated copper. The presence of this gap leads to the retention of various chemicals used in the post-plating process, and furthermore, since the solder resist cannot follow, the electrical reliability of the finally obtained printed wiring board is greatly reduced. .

JP-B-47-39895 describes a photoresist using an aqueous alkali solution containing 1 to 10 vol% of an organic solvent as a developing solution, and discloses a copolymer of methacrylic acid and methyl methacrylate, a copolymer of methyl methacrylate and itaconic acid. JP-A-59-66289 discloses a photosensitive resin composition containing a polymer or a copolymer of styrene and itaconic acid. A photosensitive resin composition containing a polymer obtained by copolymerizing an alkyl (meth) acrylate having a carbon number of 3 to 8 with a mole number of 12 to 12 is disclosed. Examination of these resin compositions revealed that, when the methacrylic acid content was increased, the electroless copper plating property was reduced and a part of the resist was peeled off, and the plating solution was contaminated and the plating rate was reduced. It was found that the physical properties of the plated copper deposited or deteriorated, and the suitable range of the methacrylic acid content was extremely narrow. Further, it has been found that there is a problem that the electric insulation property and the solder heat resistance when used as a permanent resist are insufficient.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent sensitivity and photocurability, to form efficiently by photolithography, excellent resolution and plating solution resistance, abnormal deposition of plated copper and contamination of plating solution. When used as a permanent resist, a photosensitive resin composition suitable as a photoresist for electroless copper plating excellent in solder heat resistance, electrical insulation, corrosion resistance and the like, and a method for producing a resist using the same Is to provide.

Another object of the present invention is to provide a composition having excellent sensitivity and photocurability, which can be efficiently formed by photolithography.
Excellent resolution and plating solution resistance, no abnormal deposition of plating copper and no plating solution contamination.When used as a permanent resist, it has excellent solder heat resistance, electrical insulation, electrolytic corrosion resistance, etc. An object of the present invention is to provide a photosensitive element suitable as a photoresist for electroless copper plating excellent in workability and a method for producing a plating resist.

[0013]

According to the present invention, there is provided (A) a compound represented by the following general formula (I):

[0014]

Embedded image (In the formula, R ¹ represents a divalent saturated aliphatic hydrocarbon group, R ²
And R ³ are each independently an alkyl group having 1 to 4 carbon atoms;
Represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom,
x and y each independently represent an integer of 0 to 4; ), The equivalent ratio (acid anhydride group / hydroxyl group) of the saturated or unsaturated polybasic acid anhydride to the hydroxyl group in the polyhydroxyether resin having the repeating unit represented by the formula (1) is 0.08 to 0.
8, a carboxyl group-containing polyhydroxyether resin compound obtained by reacting to have a range of 8; (B) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal; Photopolymerization initiator generating radical and (D) a compound represented by the following general formula (II)

[0015]

Embedded image (Wherein, R ⁴ , R ⁵ and R ⁶ are each independently an alkylene group, a substituted alkylene group, an alkyleneoxy group, an arylene group or a substituted arylene group, and R ⁷ , R ⁸ and R ⁹
Represents a residue obtained when an isocyanate and a compound having active hydrogen independently react with each other. ), The photopolymerization initiator for generating free radicals by actinic rays contains at least one selected from 2,4,5-triarylimidazole dimers. A photosensitive element comprising a photosensitive resin composition and a layer of the photosensitive resin composition and a support film supporting the layer.

The present invention also provides a method for producing a plating resist in which a solution of the photosensitive resin composition is coated on a substrate, dried, irradiated with imagewise actinic light, and then developed.

The present invention also provides a method for producing a plating resist, comprising laminating a layer of the photosensitive resin composition on a substrate using the above-described photosensitive element, irradiating the layer with imagewise active light, and then developing. Things.

The present invention also provides a method for producing a plating resist having one or both of an actinic ray irradiation step and a heating step after development using the photosensitive resin composition and the photosensitive element. .

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

In the photosensitive resin composition of the present invention, (A)
The polyhydroxyether resin having a repeating unit represented by the general formula (I) used to obtain the carboxyl group-containing polyhydroxyether resin compound as the component includes, for example, 0.985 to 1.015 mol of epihalohydrin and divalent polynuclear phenol 1 And a mole of an alkali metal hydroxide, for example, sodium hydroxide or potassium hydroxide 0.6 to
1.5 mol, usually in an aqueous solvent at a temperature of 10 to 50
C. by mixing until at least about 60 mol% of the epihalohydrin is consumed.

As the divalent polynuclear phenol used herein, bis (hydroxyphenyl) alkane, for example,
2,2-bis (4-hydroxyphenyl) propane,
2,4-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,2-bis ( 4
-Hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-2-chlorophenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,
3-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (2-isopropyl-4
-Hydroxyphenyl) propane, 2,2-bis (4-
(Hydroxynaphthyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) heptane, bis (4-hydroxyphenyl) ) Phenylmethane, bis (4-hydroxyphenyl)
Cyclohexylmethane, 1,2-bis (4-hydroxyphenyl) -1,2-diphenylpropane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane and the like are preferred.

Particularly preferred polyhydroxyether resins include condensation polymers derived from 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin having the following structural formula. The polyhydroxyether resin preferably has a number average molecular weight (measured by gel permeation chromatography and converted to standard polystyrene) of 10,000 to 20,000,
More preferably, it is 14000-16000. Such a polyhydroxy ether resin is a phenoxy resin (trade name UCAR Phe) from Union Carbide.
Noxy PKKH, PKHJ or PKFE).

[0023]

Embedded image The carboxyl group-containing polyhydroxyether resin compound is obtained by dissolving the above polyhydroxyether resin in a soluble organic solvent such as tetrahydrofuran, monoglyme, or dimethylformamide, and if necessary, triethylamine.
Using a catalyst such as triethylenediamine, at a temperature of 60 to 11
It is obtained by performing an addition reaction of a saturated or unsaturated polybasic anhydride at 5 ° C.

In this reaction, the equivalent ratio (acid anhydride group / hydroxyl group) of the polybasic anhydride saturated or unsaturated with respect to the hydroxyl group in the polyhydroxyether resin represented by the general formula (I) is 0. It is necessary to make the reaction be in the range of 08 to 0.8. When the equivalent ratio is less than 0.08, development residue occurs, and when the equivalent ratio exceeds 0.8, the plating solution resistance decreases.

Examples of the saturated or unsaturated polybasic anhydride to be reacted with the hydroxyl group in the above polyhydroxyether resin include phthalic anhydride, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl 2-substituted butenyltetrahydrophthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, alkenyl anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride Linoleic acid adduct of maleic anhydride, chlorendic anhydride, maleic anhydride adduct of methylcyclopentadiene, alkylated endoalkylenetetrahydrophthalic acid, trimellitic anhydride and the like.

From the viewpoint of adhesion and plating solution resistance, in addition to a saturated or unsaturated polybasic acid anhydride, a compound having one ethylenically unsaturated group and one isocyanate group (for example, ( (Meth) acryloyl isocyanate,
(Meth) ethyl acrylate isocyanate) may be reacted with a hydroxyl group of a polyhydroxyether resin having a repeating unit represented by the general formula (I). in this case,
The equivalent ratio (isocyanate group / hydroxyl group) is 0.1 to 0.5
It is preferable to carry out the reaction within the range. If the equivalent ratio is less than 0.1, the effect of improving adhesion and plating solution resistance tends to be insufficient, and if it exceeds 0.5, gelation tends to occur.

The amount of the component (A) thus obtained is preferably 20 to 90 parts by weight based on 100 parts by weight of the total of the components (A) and (B). (A)
If the amount of the component is less than 20 parts by weight, the developability, solder heat resistance, and the like tend to be poor. If it exceeds 90 parts by weight, light sensitivity, resolution, plating solution resistance, and the like tend to decrease.

As the component (B), which is a photopolymerizable unsaturated compound having at least one terminal ethylenically unsaturated group, which constitutes the photosensitive resin composition of the present invention, for example, dicyclopentenyl (meth) acrylate A compound obtained by reacting an α, β-unsaturated carboxylic acid with tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, or a polyhydric alcohol (polyethylene glycol di (meth) acrylate (where the number of ethylene groups is 2 to 2). 14), trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropaneethoxytri (meth) acrylate, trimethylolpropanepropoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate Acrylate, Tet Bisphenol A such as ramethylol methanetetra (meth) acrylate, polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Polyoxyethylene di (meth) acrylate, for example, bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, etc., glycidyl group-containing compound (Trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc.) obtained by adding α, β-unsaturated carboxylic acid to Of a polyvalent carboxylic acid (such as phthalic anhydride) with a compound having a hydroxyl group and an ethylenically unsaturated group (such as β-hydroxyethyl (meth) acrylate), an alkyl ester of acrylic acid or methacrylic acid ((meth) acrylic acid) Methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, etc.), urethane (meth) acrylate (tolylene diisocyanate and 2
A reaction product of -hydroxyethyl (meth) acrylate, a reaction product of trimethylhexamethylene diisocyanate, cyclohexane dimethanol and 2-hydroxyethyl (meth) acrylate, and the like.

The amount of component (B) used is preferably 10 to 80 parts by weight based on 100 parts by weight of the total of components (A) and (B). When the use amount of the component (B) is less than 10 parts by weight, the light sensitivity, resolution, plating solution resistance, and the like tend to decrease. If the amount exceeds 80 parts by weight, the developability, solder heat resistance, and the like tend to be poor.

The photosensitive resin composition of the present invention contains a photopolymerization initiator which generates free radicals by the actinic ray of the component (C). The amount of component (C) used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total of components (A) and (B). If the photopolymerization initiator is less than 0.1 part by weight, the photosensitivity is low, and if it exceeds 20 parts by weight, the shape of the negative pattern formed tends to be poor.

The photopolymerization initiator of the component (C) is 2,4,5-
It contains a triarylimidazole dimer as an essential component. Such materials include, for example, 2, 4, 5
-Triphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (o-ethoxyphenyl) -4,5-diphenylimidazole dimer, , 4-di (p-ethoxyphenyl) -5-phenylimidazole dimer and the like, and these compounds may be used alone or in combination of two or more.

The content of the 2,4,5-triarylimidazole dimer in the component (C) is preferably from 0.1 to 10% by weight.

In the present invention, the photopolymerization initiator may further have the general formula (III):

[0034]

Embedded image (Wherein R ¹⁰ and R ¹¹ in the formula are each a hydrogen atom or an alkyl group, and may be the same or different from each other). Examples of the compound of the general formula (III) include benzyl ketals such as benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl diisobutyl ketal, and benzyl diisopropyl ketal. These compounds may be used alone or in combination of two or more.

The content of the compound represented by the formula (III) in the component (C) is preferably 0.1 to 10% by weight.

Examples of the photopolymerization initiator which can be used as the component (C) include, for example, N, N'-tetramethyl-4,
4'-diaminobenzophenone (Michler's ketone),
Benzophenones such as N, N'-tetraethyl-4,4'-diaminobenzophenone, 2,2'-dimethoxy-
Acetophenones such as 2-phenylacetophenone, p-tert-butyldichloroacetophenone and p-dimethylaminoacetophenone; xanthones such as 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone; or hydroxycyclohexylphenyl ketone, 1- ( 4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like. These compounds may be used alone or in combination of two or more.

As the compound represented by the general formula (II) used as the component (D) in the present invention, for example, Sumidur BL-3175 (trade name of Sumitomo Bayer Urethane Co., Ltd.) is available, and the compound represented by the general formula (II) ).

In the compound represented by formula (II), R ⁴ , R ⁵ and R ⁶ are preferably an alkylene group having 1 to 15 carbon atoms, wherein the hydrogen atom of the alkylene group is a methyl group,
A substituted alkylene group substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms such as an ethyl group, an alkyleneoxy group, an arylene group having 8 to 20 carbon atoms, a hydrogen atom of an aromatic ring having a hydroxyl group,
A substituted arylene group substituted with a substituent such as an amino group or an alkyl group having 1 to 4 carbon atoms. Examples of the compound having an active hydrogen forming R ⁷ , R ⁸ and R ⁹ include oximes such as ketoxime, lactams such as ε-caprolactam, alkanols such as methanol, ethanol, isopropyl alcohol and ethoxyethanol, phenol and o. −
Nitrophenol, halogenated phenol, o-, m
And phenols such as-, p-cresol, and active methylene compounds such as acetylacetone. These active compounds react with isocyanate groups bonded to R ⁴ , R ⁵ , and R ^{6 and} are bonded to R ⁷ , R ⁸ , and R ⁹ via an —NHCO— bond. A preferred specific example of R ⁷ , R ⁸ , and R ⁹ is —ONＣＨCCH ₃ C ₂ H ₅ (a residue obtained when a ketoxime is reacted as a compound having isocyanate and active hydrogen).

The amount of the component (D) is preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the component (D) is less than 1 part by weight, plating resistance and solder heat resistance tend to be insufficient, and if it exceeds 30 parts by weight, the pattern shape becomes poor or the electroless plating solution is contaminated.

The photosensitive resin composition of the present invention may further contain other secondary components. Examples of such secondary components include, for example, a thermal polymerization inhibitor, a dye, a pigment, a coatability improver, an adhesion improver, and the like, and the selection thereof is the same as that of a normal photosensitive resin composition. It is performed under the consideration of. As a secondary component, a small amount of an epoxy resin may be contained as long as the object of the present invention is not impaired.

Next, the photosensitive element of the present invention will be described in detail.

The photosensitive element of the present invention can be obtained by laminating a layer of the photosensitive resin composition on a support film. The formation of the photosensitive resin composition layer on the support film can be performed by a conventional method. For example, the photosensitive resin composition is uniformly dissolved in an organic solvent such as methyl ethyl ketone or methylene chloride, and this solution is applied on the support film by knife coating, roll coating, spray coating, spin coating, or the like. And drying. The amount of the residual solvent in the photosensitive layer is preferably suppressed to 2% by weight or less for maintaining the characteristics.

The support film used in the present invention preferably has the heat resistance and solvent resistance required for the production of the photosensitive element. However, the release film such as a Teflon film or release paper may be used temporarily. After forming a layer of a photosensitive resin composition thereon, a film having low heat resistance or solvent resistance is laminated on this layer, and the temporary support film is peeled off. It is also possible to produce a photosensitive element having a support film having low heat resistance or low solvent resistance. Further, the support film may be transparent or opaque to actinic rays. Examples of the support film that can be used include known films such as a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film.

When a long photosensitive element is manufactured, the element is wound into a roll at the final stage of the manufacturing. In this case, using a known method with a pressure-sensitive adhesive tape or the like, by using a backing-treated support film,
The transfer of the layer of the photosensitive resin composition to the back surface of the support film when the film is wound into a roll can be prevented. For the same purpose, and further for the purpose of preventing dust from adhering, it is preferable to laminate a releasable cover film on the photosensitive resin composition layer of the photosensitive element.

Specific examples of the peelable cover film include a polyethylene film, a polypropylene film,
Teflon film, surface-treated paper, etc., when the cover film is peeled off, the adhesive strength between the photosensitive resin composition layer and the cover film is higher than the adhesive strength between the photosensitive resin composition layer and the support film. What is necessary is just a smaller thing.

The thickness of the layer of the photosensitive resin composition constituting the photosensitive element of the present invention varies depending on the thickness of the plated copper deposited by electroless plating.
0 μm.

The photosensitive resin composition of the present invention is used as a solution,
After coating on a substrate and drying, or as a photosensitive element, after laminating a layer of the photosensitive resin composition on the substrate, it is imagewise exposed and developed to form a plating resist.

Next, a method for using the photosensitive element of the present invention will be described. Lamination of the photosensitive element of the present invention on a printed wiring board is easy. That is, when there is no cover film, heating and pressure lamination are performed as it is, and when there is a cover film, the cover film is peeled off or peeled off. Heating and pressure lamination can be performed using a normal-pressure laminator known to a printed wiring board manufacturer. When the substrate has irregularities of 10 μm or more, such as a printed wiring board on which conductor wiring lines are formed, it is preferable to laminate under reduced pressure or vacuum.

An apparatus for this purpose is disclosed in Japanese Examined Patent Publication No. 53-3
There is a laminating apparatus described in Japanese Patent Publication No. 1670 and Japanese Patent Publication No. 55-13341.

In the additive method, an insulating substrate is usually used as a substrate. As the insulating substrate, a laminated substrate made of paper phenol, glass epoxy, or the like, an iron enameled substrate, a substrate having a metal core such as an aluminum plate or the like having an epoxy resin insulating layer formed on both surfaces thereof, or the like can be used. These substrates may be immersed in a solution containing a plating catalyst after drilling, and the plating catalyst may be applied to the inner wall of the through hole. As such a plating catalyst solution, a sensitizer HS-101B manufactured by Hitachi Chemical Co., Ltd. or the like can be used. It is preferable to apply an adhesive layer to the surface of the substrate 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, those known as an additive for an additive method such as a phenol-modified nitrile rubber-based adhesive can be used. Among the uncured heat-resistant resins such as epoxy resin, epoxy-modified polyimide resin, polyimide resin, and phenol resin described in JP-A-61-276875 in terms of excellent electrolytic corrosion resistance and heat resistance, epoxy resin and polyester resin It is also preferable to use an adhesive in which fine powder of a heat-resistant resin cured such as a bismaleimide-triazine resin is dispersed. In addition, there is a method of ensuring the adhesion of plated copper to the substrate by forming fine irregularities on the surface of the substrate itself. In this case, an adhesive layer is not particularly required.

A laminate in which a compound serving as a catalyst for electroless copper plating such as a Pd compound is dispersed is also a preferable substrate when electroless plated copper is deposited on the inner wall of the through hole. As a substrate in which an adhesive containing a plating catalyst is formed on the surface of a glass epoxy laminate containing a plating catalyst therein, a laminated plate ACL-E-161 manufactured by Hitachi Chemical Co., Ltd.
and so on. When such a substrate is used, a step of newly attaching a plating catalyst becomes unnecessary. It is preferable to roughen the surface of the adhesive layer before the electroless plating treatment in order to improve the adhesion of the plating catalyst or the adhesion of the electroless plated copper to be deposited. As a roughening method, there is a method of dipping in an acidic solution containing sodium dichromate or chromic acid, etc., as is well known, the roughening step is performed before the electroless copper plating step, and the photosensitive element is It may be before the lamination or after the formation of the plating resist pattern described later.

Exposure and development after lamination can be performed by a conventional method. That is, when the support film is opaque to actinic rays, 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 ultra-high-pressure mercury lamp. Heat treatment at 50 to 100 ° C. before and after exposure is preferable for improving the adhesion between the substrate and the photosensitive resin layer.

The developing solution used in the developing treatment includes 1
Using an aqueous alkaline solution containing an organic solvent of about 90% by volume as a developing solution, it can be carried out by immersing the substrate irradiated with actinic rays imagewise or by spraying the developing solution.

After forming the plating resist pattern in this manner, it is preferable to re-irradiate the active light with a light source such as a high-pressure mercury lamp or an ultra-high-pressure mercury lamp, thereby improving the chemical resistance of the plating resist. The irradiation amount of the ultraviolet rays is preferably 0.2 to 10 J / cm ^2, and it is preferable to heat to 60 to 150 ° C. during this irradiation.

Further, after the re-irradiation of the actinic ray, it is desirable to perform a heat treatment. By performing the heat treatment, the electroless copper plating solution resistance and solder heat resistance are significantly improved. The heating temperature and the heating time are, for example, 140 to 2 respectively.
20 ° C. for 30 to 90 minutes.

A step of only heating treatment may be performed without re-irradiation with actinic rays.

A solution of the photosensitive resin composition of the present invention is directly applied to a substrate by a dip coating method, a flow coating method or the like, and the solvent is dried. After lamination, in the same manner as in the case of the photosensitive element described above, imagewise exposed through a negative mask, developed, exposed to actinic rays and subjected to heat treatment to form a plating resist having excellent properties as described above. it can.

[0059]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples. In the examples and comparative examples, “parts” indicates parts by weight unless otherwise specified.

Synthesis Example 1 A in Table 1 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, a dry air introduction pipe, and a dropper and capable of heating and cooling and having a capacity of about 1 liter, and heated to 115 ° C. Warm and add B and C. After the addition of B and C, the mixture was reacted at 115 ° C. for about 15 hours, and then cooled to room temperature to obtain a solution (A-1) of a carboxyl group-containing polyhydroxyether resin compound. The equivalent ratio of the reaction in the synthesis is (acid anhydride group / hydroxyl group)
= 0.2.

[0061]

[Table 1] Synthesis Example 2 A solution of the carboxyl group-containing polyhydroxyether resin compound (A) was prepared in the same manner as in Synthesis Example 1 except that the reaction was performed in place of 16.9 parts of trimellitic anhydride. -2) was obtained. The equivalent ratio of the reaction in the synthesis is (acid anhydride group / hydroxyl group) = 0.25.

Synthesis Example 3 A in Table 2 was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, a dry air introduction pipe, and a dropper and capable of heating and cooling and having a capacity of about 1 liter, and heated to 75 ° C. Warm and raise reaction temperature to 7
While maintaining the temperature at 3 to 75 ° C, B was dripped uniformly over 0.5 hours. After the addition of B, the reaction was continued at 75 ° C. for about 4 hours.
Next, the temperature of the reaction system was lowered to 100 ° C., and C and D were added. After the addition of C and D, the mixture was reacted at 100 ° C. for about 15 hours, and then cooled to room temperature to obtain a solution (A-3) of a carboxyl group-containing polyhydroxyether resin compound having an ethylenically unsaturated group. The equivalent ratio of the reaction during the synthesis is
(Isocyanate group / hydroxyl group) = 0.25, (acid anhydride group / hydroxyl group) = 0.25.

[0063]

[Table 2] Comparative Synthesis Example A in Table 3 was placed in a reaction vessel having a capacity of about 1 liter capable of heating and cooling, equipped with a thermometer, a stirrer, a cooling pipe, a dry air introduction pipe, and a dropper, and heated to 75 ° C. Reaction temperature 7
While maintaining the temperature at 3 to 75 ° C, B was dripped uniformly over 0.5 hours. After reacting at 75 ° C. for about 4 hours after dropping B,
After cooling to room temperature, a solution (A-4) of a polyhydroxyether resin compound having an ethylenically unsaturated group was obtained. The equivalent ratio of the reaction in the synthesis is (isocyanate group / hydroxyl group) = 0.25.

[0064]

[Table 3] Examples 1-4 and Comparative Examples 1-3 The materials shown in Table 4 were blended to obtain solutions.

[0065]

[Table 4] (Note) A-1 to A-4: Solutions of the polyhydroxyether resin compounds obtained in the synthesis examples BPE-4: NK-ester manufactured by Shin-Nakamura Chemical Co., Ltd., bisphenol A polyoxyethylene dimethacrylate C-1: benzyl Dimethyl ketal C-2: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer BL-3175: trade name of block isocyanate manufactured by Sumitomo Bayern Urethane Co., Ltd. MEK: methyl ethyl ketone DMF: N, N-dimethylformamide is obtained. The solution of the photosensitive resin composition was uniformly coated on a polyethylene terephthalate film 12 having a thickness of 20 μm using the apparatus shown in FIG. 1 and dried for about 10 minutes by a hot air convection dryer 7 at 80 to 110 ° C. To remove the solvent. The dried thickness of the photosensitive resin composition layer was about 35 μm. As shown in FIG. 1, a polyethylene film 13 having a thickness of about 25 μm was further adhered on the photosensitive resin composition layer as a protective film to obtain a photosensitive element of the present invention.

In FIG. 1, 1 is a polyethylene terephthalate film feeding roll, 2 is a feed roll, 3 is a backing roll, 4 is a doctor roll, 9
And 10 are rolls, 5 is a knife, 6 is a solution of the photosensitive resin composition, 8 is a polyethylene film feeding roll, 1
1 is a photosensitive element winding roll.

The developability, photosensitive characteristics, electroless plating property after formation of the resist, plating deposition property and solder heat resistance of the obtained photosensitive element were evaluated by the following methods, and the results are shown in Table 5.

(1) Developability: Additive method substrate ACL-E manufactured by Hitachi Chemical Co., Ltd.
-168 (substrate obtained by applying a phenol-modified nitrile rubber-based adhesive containing a plating catalyst to a thickness of about 30 μm on both sides of a glass epoxy laminate containing a Pd-based plating catalyst) with a Scotch Bright manufactured by Sumitomo 3M Limited and washed with water And
Dry at 80 ° C. for 15 minutes. The photosensitive element obtained above was applied to both sides of this test substrate by Hitachi AIC's A-
Lamination was performed while peeling off the polyethylene film using a 3000 type laminator. Next, after peeling off the polyethylene terephthalate film, 500 ml of diethylene glycol mono-n-butyl ether, borax (Na ₂ B ₄ O)
₇ · 10H ₂ O) 8g, it was 40 seconds spray development at 40 ° C. in a semi-aqueous developing solution prepared at a ratio of water 500 ml. After the development, evaluation was carried out using a stereo microscope with a magnification of 30 times according to the following evaluation criteria. ：: good developability (no resin left on the substrate surface) ×: poor developability (a little resin left on the substrate surface) (2) Photosensitivity As in (1) above, A phenol-modified nitrile rubber-based adhesive containing a plating catalyst is applied to a thickness of about 30 μm on both sides of a glass epoxy laminate containing a Pd-based plating catalyst, which is a substrate for additive method ACL-E-168 manufactured by Hitachi Chemical Co., Ltd. The photosensitive element was laminated on the substrate which was peeled off using a Hitachi AIC type A-3000 type laminator. Next, Kodak Step Tablet No. 1 was placed on the polyethylene terephthalate film of the obtained sample. 2 (Eastman Kodak Co., Ltd., 21 step tablet)
Exposure was performed at 250 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. After standing at room temperature for 20 minutes, the polyethylene terephthalate film of the sample was peeled off, 200 ml of diethylene glycol mono-n-butyl ether, 8 g of borax (Na ₂ B ₄ O ₇ .10H ₂ O),
Spray development was performed at 40 ° C. for 70 seconds using a semi-aqueous developer prepared with a ratio of 800 ml of water, and the exposure required to obtain seven steps of step tablets was taken as sensitivity.

A photo tool (Kodak Step Tablet No. 2 and line / space (μm) = 30 /
30-250 / 250 (resolution) and line / space (μm) = 30 / 400-250 / 400 (adhesion)
A photo tool having a negative pattern of the above), the smallest resolution pattern to obtain a resist shape when exposed and developed with an exposure amount capable of obtaining seven steps of step tablets, obtained by closely contacting the obtained sample with a polyethylene terephthalate film. The line / space value of was taken as the resolution.

(3) Electroless Copper Plating Property In the same manner as in (1) above, the substrate ACL-E-168 (additional method substrate manufactured by Hitachi Chemical Co., Ltd.) A negative mask for test shown in FIG. 2 was brought into close contact with a polyethylene terephthalate film of a sample in which a photosensitive element was laminated on a phenol-modified nitrile rubber-based adhesive containing a catalyst to a thickness of about 30 μm). ) 250 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd.
Exposure. After standing at room temperature for 20 minutes, peeling the polyethylene terephthalate film samples, diethylene glycol mono -n- butyl ether 200 ml, borax _{(Na 2 B 4 O 7 ·} 10H 2 O) 8g, semi-aqueous developer prepared at a ratio of water 800ml The solution was spray-developed at 40 ° C for 40 seconds, and then dried at 80 ° C for 10 minutes. Then, using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., 3 J / c
Irradiation with ultraviolet rays of m ² was performed, and heat treatment was further performed at 160 ° C. for 60 minutes to obtain a test substrate on which a plating resist was formed.

The test substrate on which the plating resist was formed in this manner was immersed in a solution of 20 g of sodium dichromate in 1 liter of 42% borofluoric acid at 40 ° C. for 15 minutes to remove the exposed portion of the adhesive layer. After washing with water, the sample was immersed in 3N hydrochloric acid and washed with water. This test substrate was CuSO ₄
5H ₂ O 15 g / liter, ethylenediaminetetraacetic acid 3
0 g / liter, containing 10 ml / liter of a 37% formalin aqueous solution, immersed in an electroless copper plating solution adjusted to pH = 12.5 with NaOH at 70 ° C. for 15 hours, washed with water, and washed with 80% water.
Dry at 10 ° C. for 10 minutes. After the electroless copper plating, evaluation was performed using a stereoscopic microscope at a magnification of 30 times according to the following evaluation criteria. ：: Good electroless copper plating property (no crack, floating or peeling in resist) △: Slightly poor electroless copper plating property (crack, floating or peeling in part of resist) ×: Poor electroless copper plating (cracks, floating, peeling occurred on the entire surface of the resist) (4) Plating deposition The same operation as in (2) above was performed by Hitachi Chemical Co., Ltd. ) Additive method substrate ACL-E-168 (Pd-based plating catalyst-containing glass-epoxy laminate, on both sides of a phenol-modified nitrile rubber-based adhesive containing a plating catalyst of about 30 μm
After forming a plating resist on a substrate coated to a thickness of 3 mm, electroless copper plating is performed, and the plating deposition state of the conductor portion subjected to the electroless copper plating is evaluated using a stereoscopic microscope at a magnification of 30 times as follows. Evaluation was based on criteria. ○: Plating surface is smooth ×: Plating surface is not smooth or plating is abnormally deposited in the form of bumps or branches (5) Solder heat resistance In the same manner as in (2) above, Hitachi Chemical Co., Ltd. Additive method substrate ACL-E-168 (Pd-based plating catalyst-containing glass-epoxy laminate, on both surfaces of a phenol-modified nitrile rubber-based adhesive containing a plating catalyst of about 30 μm)
rosin flux MH-820V (Tamura Kaken Co., Ltd.) was formed on a test substrate produced by forming a plating resist on a substrate coated to a thickness of m) and electroless copper plating.
, And then immersed in a 260 ° C. solder bath for 30 seconds to perform a soldering process. Thereafter, the occurrence of cracks in the plating resist and the state of lifting and peeling of the resist from the substrate were visually evaluated according to the following criteria. Good: No cracks, floating and peeling. Bad: Cracks, floating and peeling.

[0072]

[Table 5]

[0073]

Industrial Applicability The photosensitive resin composition of the present invention and the photosensitive element using the same can be developed using a developer having a good working environment, have excellent resolution and plating solution resistance, and can be used as a permanent resist. In this case, it is suitable as a resist for electroless copper plating because of its excellent solder heat resistance.

Further, the photosensitive resin composition of the present invention and the photosensitive element using the same are excellent in chemical resistance and can be suitably used as an etching resist and a resist for electroplating.

The plating resist obtained by the present invention is excellent in solder heat resistance and chemical resistance and can be suitably used as a resist for manufacturing printed wiring boards.

[Brief description of the drawings]

FIG. 1 is a schematic view of a photosensitive element manufacturing apparatus used in Examples 1 to 4 and Comparative Examples 1 to 3.

FIG. 2 is an explanatory diagram of a test negative mask used in Examples 1 to 4 and Comparative Examples 1 to 3.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Polyethylene terephthalate film unwinding roll 2 Feed roll 3 Backing roll 4 Doctor roll 5 Knife 6 Solution of photosensitive permanent mask material 7 Dryer 8 Polyethylene film unwinding roll 9, 10 Roll 11 Photosensitive element take-up roll 12 Polyethylene terephthalate film 13 Polyethylene film 14 Photosensitive element

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/28 H05K 3/28 D (72) Inventor Yoji Tanaka 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Fumihiko Ota 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Ibaraki Research Laboratory F-term (reference) CA05 CA28 CB21 CB43 CC20 DA01 FA29 FA30 4J002 CH061 EE037 EF126 EH076 EN097 EU117 EU198 EV307 FD147 GP03 5E314 AA24 AA27 BB02 BB12 CC15 DD07 FF05 GG10 GG14

Claims (7)

[Claims] (A) The following general formula (I): (In the formula, R ¹ represents a divalent saturated aliphatic hydrocarbon group, R ²
And R ³ are each independently an alkyl group having 1 to 4 carbon atoms;
Represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom,
x and y each independently represent an integer of 0 to 4; ), The equivalent ratio (acid anhydride group / hydroxyl group) of the saturated or unsaturated polybasic acid anhydride to the hydroxyl group in the polyhydroxyether resin having the repeating unit represented by the formula (1) is 0.08 to 0.
8, a carboxyl group-containing polyhydroxyether resin compound obtained by reacting to have a range of 8; (B) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal; A photopolymerization initiator that generates a radical and (D) a compound represented by the following general formula (II): (Wherein, R ⁴ , R ⁵ and R ⁶ are each independently an alkylene group, a substituted alkylene group, an alkyleneoxy group, an arylene group or a substituted arylene group, and R ⁷ , R ⁸ and R ⁹
Each independently represents a residue obtained when an isocyanate reacts with a compound having active hydrogen. ), Wherein the photopolymerization initiator for generating free radicals by actinic rays is at least one selected from 2,4,5-triarylimidazole dimers.
A photosensitive resin composition comprising a seed. 2. A photopolymerization initiator which generates free radicals by actinic rays is represented by the general formula (III): ## STR3 ## (Wherein R ¹⁰ and R ¹¹ in the formula are each a hydrogen atom or an alkyl group, and may be the same or different from each other). The photosensitive resin composition according to claim 1, comprising at least one selected from triarylimidazole dimers. 3. A photosensitive element comprising a layer of the photosensitive resin composition according to claim 1 and a film supporting the layer. 4. The photosensitive element according to claim 3, further comprising a peelable cover film laminated on the photosensitive resin composition layer. 5. A method for producing a plating resist, comprising applying a solution of the photosensitive resin composition according to claim 1 onto a substrate, drying the solution, irradiating the solution with imagewise active light, and then developing. 6. A plating resist, comprising using the photosensitive element according to claim 3 and laminating a layer of the photosensitive resin composition on a substrate, irradiating the active image imagewise, and then developing. Manufacturing method. 7. The method for producing a plating resist according to claim 5, further comprising one or both of an actinic ray irradiation step and a heating step after the development.