JP2000047383A - Photosensitive resin composition, photosensitive element and production of plating resist using these - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. excellent in sensitivity and photosetting property and capable of efficiently forming a resist excellent in resolution and resistance to electroless copper plating by photolithography by incorporating a specified polyhydroxy-ether resin compd. and a specified blocked isocyanate compd. SOLUTION: The photosensitive resin compsn. contains 100 pts.wt., in total, of 20-90 pts.wt. polyhydroxy-ether resin compd. obtd. by allowing a polybasic acid anhydride to react with hydroxyl groups of a resin having repeating units of formula I in an equiv. ratio of 0.08-0.8 and 80-10 pts.wt. photopolymerizable unsatd. compd. having terminal ethylenically unsatd. groups, 0.1-20 pts.wt. photopolymn. initiator and 1-30 pts.wt. blocked isocyanate compd. of formula II. In the formula I, R1 is a 1-12C divalent satd. aliphatic hydrocarbon, R2 and R3 are each l-4C alkyl or the like and (x) and (y) are each an integer of 0-4. In the formula II, R4 is an m-valent org. group, (m) is an integer of 1-6 and R5 is the residue of a blocking agent.

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, and is attracting attention as a method for manufacturing a high-density printed wiring board because it is suitable for fine wiring and small-diameter through holes.

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. 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 alkaline solution, Japanese Patent Application Laid-Open No. 2-166452 discloses a copolymer of maleic anhydride and an aromatic hydrocarbon having a vinyl group with hydroxy (meth). An alkali development type resin composition represented by a resin composition containing a compound to which an acrylate is added and a carboxy group-containing epoxy acrylate is disclosed.

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.

Japanese Patent Application Laid-Open No. 5-72375 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 solution, high pH of the plating solution, and blistering or peeling of the resist when the plating time is long. And difficult to use in practical processes. Further, since a large amount of carboxylic acid remains in these resists, the pH is 12 to 1
The resist absorbs and swells in the plating solution of No. 3. 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 electroless copper plating properties, abnormal deposition of plated copper and plating solution contamination. When used as a permanent resist, solder heat resistance, electrical insulation,
An object of the present invention is to provide a photosensitive resin composition suitable as a photoresist for electroless copper plating having excellent corrosion resistance and the like, and a method for producing a resist using the same.

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 electroless copper plating properties, no abnormal deposition of plating copper and no plating solution contamination, and when used as a permanent resist, 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 resist using the same.

[0013]

The present invention provides (A) a compound represented by the following general formula (I):

[0014]

Embedded image(Where R¹Is a divalent saturated aliphatic carbon having 1 to 12 carbons
Represents a hydrogen group, R^TwoAnd R ^ThreeEach independently has 1 to 1 carbon atoms
4 alkyl groups, C 1-4 alkoxy groups or halo
X and y each independently represent an integer of 0 to 4
Represents a number. Polyamide having a repeating unit represented by)
Saturated or unsaturated with respect to the hydroxyl groups in the roxyether resin.
Equivalent ratio (acid anhydride group / hydroxyl group)
In the range of 0.08 to 0.8.
Carboxyl group-containing polyhydroxyether resin
20-90 parts by weight of compound, (B) terminal ethylenically unsaturated
A photopolymerizable unsaturated compound having at least one group
10 parts by weight (however, the total amount of component (A) and component (B) is 1
00 parts by weight. ), (C) Radiation free by actinic rays
0.1 to 20 parts by weight of a photopolymerization initiator for producing calcium (however,
And the total amount of the components (A) and (B) is 100 parts by weight.
You. ) And (D) an isocyanate represented by the following general formula (II)
Anate compounds (wherein, R^FourRepresents an m-valent organic group;
Represents an integer of 1 to 6. ) And diketo which can react with this
Oximes, phenols, alkanols and
At least one block selected from caprolactams
Represented by the following general formula (III) obtained by reacting
A blocked isocyanate compound (wherein R^FourIs m value
M represents an integer of 1 to 6;^FiveIs general
Isocyanate compounds represented by the formula (II)
Blocking agent obtained when a suitable blocking agent reacts
Represents a residue. ) In an amount of 1 to 30 parts by weight (provided that the component (A)
And the total amount of component (B) is 100 parts by weight. )
And a photosensitive resin composition.

[0015]

Embedded image The present invention also provides a photosensitive element having a layer of the photosensitive resin composition and a film supporting the layer.

The present invention also provides a method for applying a solution of the photosensitive resin composition on a substrate, drying the solution, and then irradiating the solution with an actinic light.
It is intended to provide a method for producing a plating resist which is subsequently 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 photosensitive element, irradiating the layer with an image of active light, and then developing. Is what you do.

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

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION In the photosensitive resin composition of the present invention, a polyhydroxyether having a repeating unit represented by the general formula (I) used for obtaining a carboxyl group-containing polyhydroxyether resin compound as the component (A) The resin is, for example, epihalohydrin 0.985 to 1.015.
Mol and 1 mol of a dihydric polynuclear phenol together with 0.6 to 1.5 mol of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, usually in an aqueous solvent at a temperature of 1 mol.
It can be prepared by mixing at 0-50 ° C. 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. Such a polyhydroxyether resin is available from Union Carbide. Phenoxy resin (trade name UCAR)
(Phenoxy PKKH, PLHJ or PKFE).

[0022]

Embedded image The carboxyl group-containing polyhydroxyether resin compound of the component (A) is prepared by dissolving the above polyhydroxyether resin in a soluble organic solvent such as tetrahydrofuran, monoglyme, or dimethylformamide, and optionally using a catalyst such as triethylamine or triethylenediamine. It is obtained by performing an addition reaction of a saturated or unsaturated polybasic acid anhydride at 60 to 115 ° C.

In this reaction, the equivalent ratio (acid anhydride group / hydroxyl group) of the polybasic anhydride which is 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 should be 20 to 90 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When the use amount of the component (A) is less than 20 parts by weight, developability, solder heat resistance, and the like become poor. On the other hand, when the amount exceeds 90 parts by weight, the light sensitivity, resolution, plating solution resistance and the like are reduced.

The component (B) which is a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal constituting the photosensitive resin composition of the present invention includes, 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 (meth) acrylate (where the number of ethylene groups is 2 to 14). ), Trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropaneethoxytri (meth) acrylate, trimethylolpropanepropoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate , Tetra Bisphenol A poly, such as methylol methane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Oxyethylene di (meth) acrylates, such as bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, and glycidyl group-containing compounds Compounds obtained by adding an α, β-unsaturated carboxylic acid (trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc.), polyvalent Esterified product of a carboxylic acid (such as phthalic anhydride) and 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 (methyl (meth) acrylate) Esters, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and urethane (meth) acrylate (tolylene diisocyanate
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 must be 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 photosensitivity, resolution, plating solution resistance, and the like decrease. On the other hand, when the amount exceeds 80 parts by weight, developability, solder heat resistance and the like become poor.

The photosensitive resin composition of the present invention comprises the above (A)
0.1 to 20 parts by weight of a photopolymerization initiator which generates free radicals by actinic rays of the component (C) is contained based on 100 parts by weight of the total amount of the component and (B). The photopolymerization initiator is 0.1
When the amount is less than 20 parts by weight, the light sensitivity is low.

As the photopolymerization initiator of the component (C), for example, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzophenone, N, N'-tetra Benzophenones such as methyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, and benzyldimethyl ketal (Irgacure 65 manufactured by Ciba-Geigy)
1), benzyl ketals such as benzyl diethyl ketal, 2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldicycloacetophenone, p
-Acetophenones such as dimethylaminoacetophenone, xanthones such as 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone, or hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropane-
1-one (manufactured by Merck, Darocure 1173) and the like can be used alone or in combination of two or more.

Examples of the photopolymerization initiator which can be used as the component (C) include, for example, 2,4,5-triarylimidazole dimer and 2-mercaptobenzoxazole,
Combinations with leuco crystal violet, tris (4-diethylamino-2-methylphenyl) methane and the like are also included. Additives which do not have photoinitiating property by themselves, but provide a sensitizer system having better photopolymerization initiating performance as a whole when used in combination with the above substances, such as triethanolamine for benzophenone. Can be used.

As the isocyanate compound represented by the general formula (II) used for obtaining the blocked isocyanate compound of the component (D), the isocyanurate type represented by the general formula (IV) or the isocyanurate type represented by the general formula (V) Examples thereof include a biuret type represented by the general formula (VI) and an adduct type represented by the general formula (VI), and an isocyanurate type having an isocyanate skeleton is particularly preferable from the viewpoint of adhesion.

[0033]

Embedded image (R ^{6 to} R ¹⁴ in the general formulas IV, V and VI are each independently an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 4 to 6 carbon atoms, and the alkylene group and the cycloalkylene group are A divalent hydrocarbon group or an arylene group having 6 to 14 carbon atoms, wherein the hydrogen atom of the group has 1 to 3 carbon atoms.
May be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Specific examples of the divalent hydrocarbon group having an alkylene group and a cycloalkylene group include the following.

[0034]

Embedded image Examples of the blocking agent include at least one compound selected from diketones, oximes, phenols, alkanols, and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.

Further, m in the general formulas (II) and (III)
Is an integer of 1 to 6, and when m is 7 or more, it is difficult to obtain a commercial product.

The amount of component (D) used is 1 to 30 parts by weight based on 100 parts by weight of the total of components (A) and (B). When the component (D) is less than 1 part by weight, plating resistance,
Solder heat resistance becomes 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 produce 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 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 process 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 the formation of the plating resist pattern in this manner, it is preferable to re-irradiate active rays using 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, it is desirable to carry out a heat treatment after re-irradiation with actinic rays. 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.

Further, 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.

[0055]

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 of the carboxyl group-containing polyhydroxyether resin compound (A-1). The equivalent ratio of the reaction in the synthesis is (acid anhydride group / hydroxyl group)
= 0.2.

[0057]

[Table 1] Synthesis Example 2 A carboxyl group-containing polyhydroxy ether resin compound (A-2) 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. ) 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 carboxyl group-containing polyhydroxyether resin compound having an ethylenically unsaturated group (A
-3) was obtained. The equivalent ratio of the reaction during the synthesis is
(Isocyanate group / hydroxyl group) = 0.25, (acid anhydride group / hydroxyl group) = 0.25.

[0059]

[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 of the polyhydroxyether resin compound (A-4) having an ethylenically unsaturated group was obtained. The equivalent ratio of the reaction in the synthesis is (isocyanate group / hydroxyl group) = 0.25.

[0060]

[Table 3] Examples 1 to 5 and Comparative Examples 1 to 2 The materials shown in Table 4 were blended to obtain solutions.

[0061]

[Table 4] Components (A), (B) and (D) shown in Table 5 were added to this solution to prepare a solution of the photosensitive resin composition.

[0062]

[Table 5] * 1: NK-ester, bisphenol A polyoxyethylene dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. * 2: Trade name of block isocyanate having the following structure manufactured by Sumitomo Bayer Urethane Co., Ltd.

[0063]

Embedded image The obtained solution of the photosensitive resin composition is uniformly coated on a polyethylene terephthalate film 12 having a thickness of 20 μm using the apparatus shown in FIG. 1, and is heated for about 10 minutes by a hot air convection dryer 7 at 80 to 110 ° C. Dry 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 of the obtained photosensitive element, the electroless plating property after formation of the resist, the plating deposition property, and the solder heat resistance were evaluated by the following methods. The results are shown in Table 6.

(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 70 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 substrate surface) ×: Poor developability (residual resin left on substrate surface) (2) Electroless copper plating properties Similarly, a phenol-modified nitrile rubber-based adhesive containing a plating catalyst having a thickness of about 30 μm is applied to both surfaces of a substrate for an additive method ACL-E-168 (a Pd-based plating catalyst-containing glass epoxy laminate) manufactured by Hitachi Chemical Co., Ltd. The test negative mask shown in FIG. 2 was brought into close contact with the polyethylene terephthalate film of the sample in which the photosensitive element was laminated on the substrate coated with the photosensitive element, and 250 mJ / cm using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. ^Two
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 70 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) (3) 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) (4) Solder heat resistance In the same manner as in (2) above, Hitachi Chemical A phenol-modified nitrile rubber-based adhesive containing a plating catalyst is applied on both sides of a glass epoxy laminate containing a Pd-based plating catalyst to about 30 μm on a substrate for additive method ACL-E-168 manufactured by Kogyo Co., Ltd.
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 state of occurrence of plating resist cracks 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.

[0068]

[Table 6]

[0069]

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 sensitivity and photocurability, and have high resolution and electroless copper plating. When used as a permanent resist, 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 of the present invention has excellent 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 diagram of an apparatus for manufacturing a photosensitive element used in Examples 1 to 5 and Comparative Examples 1 and 2.

FIG. 2 is an explanatory diagram of a test negative mask used in Examples 1 to 5 and Comparative Examples 1 and 2.

[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 Continuing on the front page (72) Inventor Yoji Tanaka 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd. (72) Inventor Fumihiko Ota 4--13 Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 F term in Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. FA50 5E343 AA07 AA15 AA17 AA22 BB24 CC02 CC62 CC71 DD33 GG16 GG20

Claims (7)

[Claims] (A) The following general formula (I):(Where R¹Is a divalent saturated aliphatic carbon having 1 to 12 carbons
Represents a hydrogen group, R^TwoAnd R ^ThreeEach independently has 1 to 1 carbon atoms
4 alkyl groups, C 1-4 alkoxy groups or halo
X and y each independently represent an integer of 0 to 4
Represents a number. Polyamide having a repeating unit represented by)
Saturated or unsaturated with respect to the hydroxyl groups in the roxyether resin.
Equivalent ratio (acid anhydride group / hydroxyl group)
In the range of 0.08 to 0.8.
Carboxyl group-containing polyhydroxyether resin
20-90 parts by weight of compound, (B) terminal ethylenically unsaturated
A photopolymerizable unsaturated compound having at least one group
10 parts by weight (however, the total amount of component (A) and component (B) is 1
00 parts by weight. ), (C) Radiation free by actinic rays
0.1 to 20 parts by weight of a photopolymerization initiator for producing calcium (however,
And the total amount of the components (A) and (B) is 100 parts by weight.
You. ) And (D) an isocyanate represented by the following general formula (II)
Anate compounds (wherein, R^FourRepresents an m-valent organic group;
Represents an integer of 1 to 6. ) And diketo which can react with this
Oximes, phenols, alkanols and
At least one block selected from caprolactams
Represented by the following general formula (III) obtained by reacting
A blocked isocyanate compound (wherein R^FourIs m value
M represents an integer of 1 to 6;^FiveIs general
Isocyanate compounds represented by the formula (II)
Blocking agent obtained when a suitable blocking agent reacts
Represents a residue. ) In an amount of 1 to 30 parts by weight (provided that the component (A)
And the total amount of component (B) is 100 parts by weight. )
Photosensitive resin composition. Embedded image 2. The photosensitive resin composition according to claim 1, wherein the isocyanate compound represented by the general formula (II) is a compound having an isocyanurate skeleton represented by the following formula. Embedded image (Wherein, R ⁶ , R ⁷ and R ⁸ each independently represent an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 1 to 12 carbon atoms, or a divalent having the alkylene group and the cycloalkylene group) A hydrocarbon group or an arylene group having 6 to 14 carbon atoms, wherein the hydrogen atom of the group may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.) 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.