JP2002290016A - Method of manufacturing composite member, photosensitive composition, insulator, and composite member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a composite member with which a conductive section in which a conductive circuit can be designed with a high degree of freedom, an insulator is not deteriorated by exposure, no abnormal deposition of a metal occurs on the insulator and which has a fine pattern can be formed easily. SOLUTION: This method of forming composite member includes a step of forming a photosensitive composition layer 2 containing a photooxidizer and a macromolecular compound which generates an ion-exchange group under the presence of an acid on an insulator 1, a step of generating the acid in exposed sections 4 by exposing the photosensitive composition layer 2 to a pattern, and a step of generating the ion-exchange group from the acid generated in the exposed sections by exposing the layer 2 to the pattern. This method also includes a step of forming the conductive section by coupling metallic ions or a metal with the pattern of the ion-exchange group formed through the exposure to the pattern. The macromolecular compound is composed of a copolymer containing a first repeating unit having the ion- exchange group and a second repeating unit which is not dissolved by the acid and has an alkali-insoluble group, and at least part of the ion-exchange group is protected by a protecting group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a composite member, which is used for a wiring board or the like in the fields of electricity, electronics, communications, etc., in which a conductive portion such as wiring is formed on an insulator, The present invention relates to a photosensitive composition which can be suitably used in a production method, an insulator for producing a composite member, and a composite member.

[0002]

2. Description of the Related Art In recent years, high integration and miniaturization of various electric and electronic parts including semiconductors have been advanced. It is certain that the trend will continue to increase in the future. Along with this, fine patterns, fine pitches, three-dimensional wirings, and the like of metal wirings have been attempted in order to perform high-density mounting even on printed wiring boards.

In particular, three-dimensional wiring is indispensable for high-density mounting, and various methods have been proposed for manufacturing a wiring board having three-dimensional wiring.

However, according to the conventional method of manufacturing a wiring board, it has been difficult to easily form fine three-dimensional wiring having a three-dimensionally free shape.

In forming a three-dimensional wiring on a wiring board, a two-dimensional wiring board is laminated to form a multilayer wiring board structure as typified by, for example, a build-up wiring board. In such a multilayer wiring board structure, adjacent wiring layers are connected by a conductive column called a via.

Conventionally, such vias have been formed by the following method. First, through holes (via holes) are provided in an insulator by a photolithography process using a photosensitive polyimide, a resist, or the like. Then
Vias are formed by selectively plating or filling the holes with conductive paste. To form a via by such a method, steps of resist application, exposure, and etching are required. Therefore, it is troublesome and it is difficult to improve the yield.

As another example of a method for forming a via, there is a method in which a via hole of a predetermined size is provided in an insulator by using a drill or a CO ₂ laser, and the hole is plated or filled with a conductive paste. No.

However, it is difficult to freely form a fine via of several tens of microns or less at a desired position by such a method of piercing the insulator.

In the method described in JP-A-7-207450, a compound having a hydrophilic group is introduced into the pores of a three-dimensional porous film such as PTFE, and in this state, a low-pressure mercury lamp (with a wavelength of 185 nm and a wavelength of 185 nm) is used. (254 nm). Thereby, a hydrophilic group is formed on the three-dimensional porous film. Further, metal plating is performed on the three-dimensional porous film.

However, in the above-mentioned method, since the exposure is performed with light having a short wavelength, the material constituting the three-dimensional porous film is deteriorated. Further, there is a problem that the exposure light is absorbed by the three-dimensional porous film and the exposure light does not penetrate into the inside of the porous body, so that a fine via cannot be formed.

Japanese Patent Application Laid-Open No. H11-24977 describes another method of forming a via. In this method, first, a photosensitive composition containing a photosensitive reducing agent and a metal salt is impregnated on the entire surface of an insulator made of a porous material. Then, by performing post-pattern exposure,
The cation of the metal salt in the exposed part is reduced to a metal nucleus. Thereafter, the photosensitive composition in the unexposed portions is washed away, and the remaining metal nuclei are subjected to electroless plating or soldering to form vias having a desired pattern.

However, in this method, since the entire surface of the insulator made of a porous material is impregnated with the photosensitive composition containing the metal salt, the metal salt adsorbed on the portion corresponding to the unexposed portion is completely removed after the exposure. It is difficult to remove. Therefore, in the subsequent reduction step, a phenomenon occurs in which metal nuclei are deposited on undesired portions. Such abnormal deposition of metal nuclei causes problems in the insulating properties between adjacent vias and wiring layers as the pattern becomes finer.

[0013]

SUMMARY OF THE INVENTION The present invention has a high degree of freedom in designing a conductive circuit, does not cause deterioration of an insulator due to exposure, and has a fine pattern having no abnormal deposition of metal on the insulator. It is an object of the present invention to provide a method for manufacturing a composite member in which a portion can be easily formed.

Another object of the present invention is to provide a photosensitive composition and an insulator for use in manufacturing the above-described composite member.

Another object of the present invention is to provide a composite member manufactured by the above-described method.

[0016]

In order to solve the above-mentioned problems, the present invention relates to a method for producing a composite member in which a conductive portion is selectively formed on an insulator, comprising: (1) a photoacid generator; When,
Forming a photosensitive composition layer containing a polymer compound that generates an ion-exchange group in the presence of an acid on the insulator; and (2) pattern-exposing the photosensitive composition layer, (3) generating an ion-exchange group with an acid generated in the exposed portion of the photosensitive composition layer by the pattern exposure; and (4) forming ions by the pattern exposure. Forming a conductive portion by bonding a metal ion or metal to the pattern of the exchangeable group, wherein the polymer compound is not decomposed by an acid and a first repeating unit having an ion exchange group. A method for producing a composite member, comprising: a copolymer containing a second repeating unit having an alkali-insoluble group, wherein part or all of the ion-exchange group is protected by a protecting group. Offer To.

The present invention also provides a photoacid generator, a polymer compound having a compound capable of forming an ion-exchange group in the presence of an acid, and a photosensitizer. A photosensitive composition which is photosensitive, wherein the polymer compound includes a first repeating unit having an ion-exchange group and a second repeating unit having an alkali-insoluble group which is not decomposed into an acid. Provided is a photosensitive composition for producing a composite member, which is a polymer, wherein a part or all of the ion-exchange group is protected by a protecting group.

Further, the present invention provides a porous insulator, wherein the insulator has an inner hole surface coated with the above-mentioned photosensitive composition. I will provide a.

Still further, the present invention provides a composite member manufactured by the above method.

The present inventors have conducted intensive studies on a method of manufacturing a composite member having a fine conductive pattern and found the following findings. That is, in the photosensitive composition, by separating the two reactions of the exposure reaction by light and the reaction that generates an ion-exchange group, the wavelength that is different from the wavelength that the base or the compound that generates the ion-exchange group absorbs, It was found that exposure could be performed at an exposure wavelength having excellent light transmittance. In addition, two types of groups, a repeating unit having an ion-exchangeable group and a repeating unit having an alkali-insoluble group that is not decomposed by an acid, are mixed in a polymer compound, so that ion exchange and adhesion to a substrate can be achieved. It was found that resolution performance could be improved by sharing the role of. Accordingly, the present invention has been made to easily and inexpensively manufacture a composite member in which a fine conductive portion is selectively formed on an insulator.

First, the concept of the present invention will be described. As an example, a method for forming a metal three-dimensional wiring on the surface and inside of a porous insulator will be described as an example, but this is simplified for the sake of understanding, and the present invention is not limited to this. is not.

In the present invention, a conductive pattern is formed on the surface layer and inside of a substrate made of a porous material of nanometer order to micron order. The base material used here is required to have low heat resistance and a low dielectric constant to some extent. A material satisfying these conditions has a large absorption for ultraviolet light, and therefore, it is difficult to perform exposure with ultraviolet light. Therefore, the present inventors have designed a system that causes a photoreaction at a wavelength different from the absorption wavelength of the substrate.

The photosensitive composition used in the present invention contains a photoacid generator and a polymer compound that generates an ion-exchange group in the presence of an acid. As the photoacid generator, one that responds to various wavelengths can be selected depending on the type.
Therefore, a photoacid generator sensitive to a wavelength other than the wavelength at which the substrate absorbs a large amount of light can be appropriately selected and used. Furthermore, in the case of a substrate having a large absorption at all wavelengths of 450 nm or less, such as polyimide, the addition of a photosensitizer makes it possible to sensitize with light of 500 nm or more.

The acid generated by light acts on a compound that generates a chemically protected ion-exchange group to cause a deprotection reaction, thereby generating an ion-exchange group. For this reason,
The ion-exchange group is selectively present in the exposed portion subjected to the pattern exposure. Since pattern exposure is performed using a wavelength at which the absorbance of the insulator is low, the inside of the insulator is also exposed if the insulator is porous.

Next, a metal ion or a metal is bonded to the ion-exchange group formed in the exposed portion by the pattern exposure. Further, a conductive portion is formed by reducing the metal ions bonded to the ion-exchangeable groups in the exposed portions to metallize the metal ions.

Subsequently, electroless plating is performed on the conductive portion formed on the exposed portion to improve conductivity. As a result, a porous insulator having a three-dimensional metal wiring on the surface and inside can be obtained.

The polymer compound which generates an ion-exchange group in the presence of an acid used in the present invention comprises a first repeating unit having an ion-exchange group and an alkali-insoluble second repeating unit which is not decomposed by an acid. And a repeating unit of
The presence of the second repeating unit prevents the photosensitive composition layer from being eluted in a subsequent step of binding a metal or metal ion, and can produce a composite member having a fine pattern. .

Hereinafter, the present invention will be described in detail.

First, a method for manufacturing a composite member will be described.

The method of manufacturing a composite member according to the present invention will be described with reference to an example in which a conductive portion is formed in a sheet-like insulator in a plane direction and a thickness direction.

A conductive portion having a fine pattern is formed on an insulator. Here, a photosensitive composition containing a photoacid generator and a polymer compound that generates an ion-exchange group in the presence of an acid is used, and a porous insulator is used in a plane direction and a thickness direction of a sheet-shaped insulator. A case of forming a composite member having a fine conductive pattern will be described.

In the present invention, a photosensitive composition containing a photoacid generator and a polymer compound that forms an ion-exchange group in the presence of an acid is used. That is, as described above, the photosensitive composition layer is subjected to pattern exposure with visible light or ultraviolet light to generate an acid in the exposed portion, and an ion exchange group is generated by the generated acid. Since such a composition is used, the absorption wavelength and the exposure wavelength of the substrate and the photosensitive composition can be greatly different.

Here, the photoacid generator is a compound that generates an acid upon irradiation with actinic radiation.

The photoacid generator used in the present invention includes:
Triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, diphenyliodonium triflate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium triflate, bis (4-tert
-Butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-tert-butylphenyl) iodoniumnaphthalenesulfonate, bis (4-tert
-Butylphenyl) iodoniumhexafluoroantimonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, 1- (naphthylacetomethyl) thiolanium triflate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium triflate, dicyclohexyl ( 2-oxocyclohexyl) sulfonium triflate, dimethyl (2-oxocyclohexyl) sulfonium triflate, S-
(Trifluoromethyl) dibenzothiophenium trifluoromethanesulfonic acid, iodonium salts such as Se- (trifluoromethyldibenzothiophenium trifluoromethanesulfonic acid, I-dibenzothiophenium trifluoromethanesulfonic acid, sulfonium salts, phosphonium salts, Onium salts such as diazonium salts and pyridinium salts; 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,21-naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4-tetrahydrobenzophenone, 1,1,1 1,3-Diketo-2-diazo compounds such as 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1-tris (4-hydroxyphenyl) ethane, diazoketonization of diazobenzoquinone compounds, diazonaphthoquinone compounds, etc. Containing haloalkyl groups such as 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -S-triazine, naphthyl-bis- (trichloromethyl) -S-triazine Halogen-containing compounds such as hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds; sulfone compounds such as β-ketosulfone such as 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane; and βsulfonylsulfone; 2
-[2- (5-methylfuran-2-yl) ethenyl]-
4,6-bis (trichloromethyl) -s-triazine,
2- [2- (furan-2-yl) ethenyl] -4,6-
Bis (trichloromethyl) -s-triazine, 2- [2
-(4-Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylaminoethyl) amino] -4,6-bis (trichloromethyl ) -S-Triazine dimethyl sulfate, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-dimethoxyphenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)
And triazine compounds such as -s-triazine and 2,4,6-tris (trichloromethyl) -s-triazine.

Of these compounds, a polycyclic aromatic compound in which the aromatic ring is conjugated is more preferable because the absorption wavelength shifts to the longer wavelength side.

The conjugated complex aromatic ring means that a plurality of aromatic rings have a conjugated and defined molecular structure. Here, conjugate refers to a state in which every other double bond is aligned in a state close to a plane.

Examples of such conjugated complex aromatic rings include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, naphthacene ring, chrysene ring, 3,4-benzophenanthrene ring, perylene ring, pentacene ring and picene ring. No. In addition, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an indole ring, a benzoxazole ring, a benzothiazole ring, an indazole ring, a chromene ring, a quinolindinnoline ring, a phthalazine ring, a quinazoline ring, a dibenzofuran ring, a carbazole ring, an acridine ring, Examples include a nanthridine ring, a phenanthroline ring, a phenazine ring, a thianthrene ring, an indolizine ring, a naphthyridine ring, a purine ring, a pteridine ring, and a fluorene ring. In particular, when the aromatic ring is selected from a naphthalene ring, an anthracene ring, and a phenanthrene ring, transparency and dry etching resistance are high, which is preferable. Such a conjugated complex aromatic ring can be introduced into the main chain skeleton or side chain skeleton of the photoacid generator. Alternatively, a conjugated complex aromatic ring may be introduced into the main chain skeleton or side chain skeleton of the photosensitizer described later.

Specifically, examples of the photoacid generator include an onium salt having a naphthalene skeleton or a dibenzothiophene skeleton, a sulfonate, a sulfonyl, and a sulfamide compound. As a more specific example,
Onium salts of naphthalene-containing sulfonium salts such as NAT-105 and NDS-105, naphthalene-containing chlorinated triazines such as NDI-106, and sulfonamides such as naphthalidyl triflate (these are green chemicals) dibenzothiophene derivatives (Daikin Chemical) ), And compounds such as naphthalene bisulfone.

The amount of the photoacid generator to be added to the ion-exchange polymer compound is preferably at least 0.1% and less than 20%. If the amount of the photoacid generator is less than 0.1%, the sensitivity may be lowered. If the amount is more than 20%, the coating film performance is remarkably deteriorated and elutes in the plating solution which is an alkaline solution during plating. This is because there is a risk of doing so.

When sufficient sensitivity cannot be obtained with the photoacid generator alone, or when exposure with longer wavelength light is desired, a photosensitizer may be added. The photosensitizer is not particularly limited as long as it can photosensitize a compound that generates an ion-exchange group by exposure as described above, and is appropriately selected according to the type of the compound to be used, the light source, and the like. You.

Specific examples of the sensitizer include, for example, aromatic hydrocarbons and derivatives thereof, benzophenone and derivatives thereof, o-benzoyl benzoate and derivatives thereof, acetophenone and derivatives thereof, benzoin and benzoin ether and derivatives thereof, Xanthone and its derivatives, thioxanthone and its derivatives disulfide compounds, quinone compounds, halogenated hydrocarbon-containing compounds and amines, 3-ethyl-5-[(3
-Ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2-thioxo-4-oxoazolidinone, 5-
[(1,3-dihydro-1,3,3-trimethyl-2H
-Indole-2-ylidene) ethylidene] -3-ethyl-2-thioxo-4-oxazolidinone and other merocyanine dyes, 3-butyl-1,1-dimethyl-2-
[2 [2-diphenylamino-3-[(3-butyl-
1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-
Cyclopenten-1-yl] ethenyl] -1H-benz [e] indolium percolate, 2- [2- [2
-Chloro-3-[(3-ethyl-1,3-dihydro-
1,1-dimethyl-2H-benz [d] indole-2
-Ylidene) ethylidene] -1-cyclohexene-1-
Yl] ethenyl] -1,1-dimethyl-3-ethyl-1
H-benz [e] indolium tetrafluoroborate, 2- [2- [2-chloro-3-[(3-ethyl-
1,3-dihydro-1,1-dimethyl-2H-benz [e] indole-2-ylidene) ethylidene] -1-
Cyclopenten-1-yl] ethenyl] -1,1-dimethyl-3-ethyl-1H-benz [e] indolium
Cyanine dyes such as iodide, squarium cyanine dyes, 2- [p- (dimethylamino) styryl]
Benzothiazole, 2- [p- (dimethylamino) styryl] naphtho [1,2-d] thiazole, 2-[(m-
Hydroxy-p-methoxy) styryl] benzothiazole and other styryl dyes, eosin B (CI No.
45400), Eosin J (CI No. 4538)
0), cyanosine (CI No. 45410), bengal rose, erythrosine (CI No. 4543)
0), 2,3,7-trihydroxy-9-phenylxanthen-6-one, xanthene dyes such as rhodamine 6G, thionin (CI No. 52000), Azure A
(C.I. No. 52005), Azure C (C.I.N.
o. Thiazine dyes such as 52002), pyronin B
(CI No. 45005), pyronin GY (C.I.
I. No. A pyronin dye such as 45005), 3-acetylcoumarin, 3-acetyl-7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, and 3- (2-benzothiazolyl) -7.
-(Dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethylamino) coumarin, 10-
(2-benzothiazolyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 1
1H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 3- (2-benzothiazolyl) -7
-(Dioctylamino) coumarin, 3-carbethoxy-
7- (diethylamino) coumarin, 10- [3- [4-
(Dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro-1,1,1
Coumarin-based dyes such as 7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, and 3,3′-carbonylbis (7-diethylaminocoumarin) Ketocoumarin-based dyes such as 3,3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin and 3,3'-carbonylbis (7-dibutylaminocoumarin); 4- (dicyanomethylene) -2-methyl-6-
(P-dimethylaminostyryl) -4H-pyran, 4-
Examples include DCM dyes such as (dicyanomethylene) -2-methyl-6- (p-dibutylaminostyryl) -4H-pyran.

The mixing ratio of such a photosensitizer is usually 0.001 to 10 with respect to the molar concentration of the photoacid generator.
mol, preferably 0.1 to 1 mol.

In the present invention, the polymer compound which forms an ion-exchange group by an acid-catalyzed reaction in the presence of an acid is the same as the first repeating unit having an ion-exchange group, which is not decomposed into an acid and is insoluble in an alkali. A copolymer comprising a second repeating unit having a group is used.

Specific examples of the first repeating unit having ion exchange properties include novolak resins such as phenol novolak and naphthol novolak, polyisobornene, polynorbornene, polycyclohexene, polycyclopentene, polycycloheptene, and polycyclooctene. Some of the side chains of the main chain alicyclic polymer, such as, those substituted with a carboxyl group or a sulfonyl group, phenol resins such as polyhydroxystyrene and polyhydroxyvinylnaphthalene, and poly-α-chloroacrylate and polycyanoacrylate. Examples include a repeating unit of a molecular compound. Further, a resin in which a hydroxyl group of a novolak resin or a phenol resin is substituted with a sulfonyl group can also be used.

The first repeating unit is required to have a part or all of the ion-exchange group protected by a protecting group which is eliminated by an acid as described later. The acid generated from the photoacid generator upon exposure removes the protecting group protecting the ion-exchange group, thereby generating an ion-exchange group and allowing the exposed portion to adsorb metal ions.
As a result, a metal pattern according to the light pattern can be transferred.

The second repeating unit which is not decomposed by an acid and has an alkali-insoluble group includes, for example, main chain alicyclic ring such as polyisobornene, polynorbornene, polycyclohexene, polycyclopentene, polycycloheptene and polycyclooctene. Polymers and those in which a part of their side chains are substituted with an alkyl group, α-methylstyrene, polystyrene, polyvinylnaphthalene, polymethylmethacrylate, polymethylacrylate, isobornylmeth (a) acrylate, menthylmeth (a) acrylate, norbornylmetha ( A) Polymethacrylates such as acrylates, adamantyl meth (a) acrylates, allyl meth (a) acrylates, naphthol meth (a) acrylates, etc. Nothing, polysilanes, polyesters, polyamides, groups having polarity, such as polyimides include repeating units of the polymer compound of those not appear in the side chain.

A copolymer obtained by copolymerizing the first and second repeating units as described above is used in the present invention as a polymer compound. Usually, a photosensitive composition used for a resist for processing an electronic device is required to be dissolved in a developer in order to resolve a pattern. On the other hand, in the present invention, the polymer compound which is a main component of the photosensitive composition needs to remain on the surface of the porous body even after immersion in an alkali solution of a plating solution used in a later necessary plating step. There is. Therefore, the object of the present invention cannot be achieved with a polymer compound that elutes in an alkaline solution of a plating solution.

In the polymer compound according to the present invention, since the ion-exchange group contained in the first repeating unit is a polar group, it exhibits alkali solubility after the step of decomposing the protecting group with an acid. Metal ionic acid serving as a nucleus for plating is adsorbed to this portion. Since plating grows catalytically with metal ions as nuclei, polar groups to which ions are adsorbed need not be present in all repeating units of the polymer compound. On the other hand, by being a hydrophobic repeating unit and a copolymer that is not decomposed into an acid, it is possible to prevent the polymer compound from being eluted during plating even after the step of decomposing the protective group by the acid.

The ratio of the first repeating unit having an ion-exchangeable group to the second repeating unit having a group which is not decomposed by an acid and insoluble in an alkali is 10:90 to 75:25.
(Mol ratio). When the number of the first repeating units having a polar group is less than the above range, the generation of plating nuclei does not proceed, and it becomes difficult to sufficiently promote plating. On the other hand, when the number of the second repeating units having no polar group is less than the above range, the second repeating units may be eluted in the plating solution and plating may not proceed. In order to transfer a finer plating pattern, the ratio between the first repeating unit and the second repeating unit should be 20:80 to 5
More preferably, it is between 0:50.

The weight average molecular weight (Mw) of the polymer compound in terms of polystyrene can be changed according to the desired characteristics of the photosensitive composition, but it is 2,000 to 150,000.
Is preferably in the range of 10,000 to 80,
000 is more preferable. Mw is. 2,000
If the amount is less than the above, the film-forming property and the adhesion to the porous body may be deteriorated. On the other hand, when Mw exceeds 150,000, resolution, plating characteristics, and the like tend to deteriorate. Also,
The molecular weight dispersity Mw / Mn of the polymer compound is preferably from 1 to 5, more preferably from 1 to 3.

Examples of the protecting group capable of leaving with an acid include t-butyl, t-butoxycarbonyl, acetyl, 1-methoxyethyl, 1-ethoxyethyl,
1-butoxyethyl group, 1-pentoxyethyl group, tetrahydropyranyl group, methyltetrahydropyranyl group,
Examples thereof include a tetrahydrofuranyl group, a methyltetrahydrofuranyl group, a carboxybutoxymethyl group, a carboxybutoxyethyl group, a carboxybutoxypropyl group, and a trialkylsilyl group. Among them, t-butyl group, t-butoxycarbonyl group, 1-ethoxyethyl group, 1-butoxyethyl group, tetrahydropyranyl group,
A methyltetrahydropyranyl group, a tetrahydrofuranyl group and a methyltetrahydrofuranyl group are preferred.

Examples of the substituent capable of leaving with an acid include esters such as t-butyl ester, isopropyl ester, ethyl ester, methyl ester, and benzyl ester; ethers such as tetrahydropyranyl ether; and t-butoxycarbo. Alkoxycarbonates such as carboxylate, methoxycarbonate and ethoxycarbonate; silyl ethers such as trimethylsilyl ether, triethylsilyl ether and triphenylsilyl ether; isopropyl ester, tetrahydropyranyl ester, tetrahydrofuranyl ester, methoxyethoxymethyl ester , 2-trimethylsilylethoxymethyl ester, 3-oxocyclohexyl ester, isobornyl ester, trimethylsilyl ester, triethyl Ryl ester, isopropyldimethylsilyl ester, di-t-butylmethylsilyl ester, oxazole, 2-alkyl-1,3-oxazoline, 4-alkyl-5-oxo-1,3-oxazoline, 5-alkyl-4-oxo-1 Esters such as 2,3-dioxolane, t-butoxycarbonyl ether,
t-butoxymethyl ether, 4-pentenyloxymethyl ether, tetrahydropyranyl ether, tetrahydrothiopyranyl ether, 3-bromotetrahydropyranyl ether, 1-methoxycyclohexyl ether, 4-methoxytetrahydropyranyl ether, 4-
Methoxytetrahydrothiopyranyl ether, 1,4-
Dioxan-2-yl ether, tetrahydrofuranyl ether, tetrahydrothiofuranyl ether, 2,
3,3a, 4,5,6,7,7a-octahydro-7,
8,8-trimethyl-4,7-methanobenzofuran-2
Ethers such as -yl ether, t-butyl ether, trimethylsilyl ether, triethylsilyl ether, triisopropylsilyl ether, dimethylisopropylsilyl ether, diethylisopropylsilyl ether, dimethylsexylsilyl ether, t-butyldimethylsilyl ether, methylene acetal, Acetals such as ethylidene acetal and 2,2,2-trichloroethylidene acetal, ketals such as 1-t-butylethylidene ketal, isopropylidene ketal (acetonide), cyclopentylidene ketal, cyclohexylidene ketal and cycloheptylidene ketal , Methoxymethylene acetal, ethoxymethylene acetal, dimethoxymethylene orthoester, 1-
Cyclic orthoesters such as methoxyethylidene orthoester, 1-ethoxyethylidene orthoester, 1,2-dimethoxyethylidene orthoester, 1-N, N-dimethylaminoethylidene orthoester, 2-oxacyclopentylidene orthoester, and trimethylsilyl Silyl ketene acetals such as silyl ketene acetal, triethylsilyl ketene acetal, t-butyldimethylsilyl ketene acetal, di-t-
Butylsilyl ether, 1,3-1 ′, 1 ′, 3 ′,
Silyl ethers such as 3′-tetraisopropyldisiloxanilidene ether, tetra-t-butoxydisiloxane-1,3-diylidene ether, dimethyl acetal, dimethyl ketal, bis-2,2,2-trichloroethyl acetal, Acyclic acetals and ketals such as bis-2,2,2-trichloroethyl ketal, diacetyl acetal and diacetyl ketal;
1,3-dioxane, 5-methylene-1,3-dioxane, 5,5-dibromo-1,3-dioxane, 1,3-
Dioxolane, 4-bromomethyl-1,3-dioxolane, 4-3′-butenyl-1,3-dioxolane,
Examples include cyclic acetals and ketals such as 4,5-dimethoxymethyl-1,3-dioxolane, and cyanohydrins such as O-trimethylsilyl cyanohydrin, O-1-ethoxyethyl cyanohydrin, and O-tetrahydropyranyl cyanohydrin. it can.

Introduction rate of a protecting group which is easily removed by the action of an acid into a polymer compound (an acidic functional group in a polymer compound which becomes an ion-exchangeable group by removing a protecting group by the action of an acid) (The ratio of the number of protected acidic functional groups to the total number of protected acidic functional groups) cannot be determined unconditionally depending on the type of the protective group or the ion-exchange polymer compound.
The content is 5 to 100 mol%, more preferably 20 to 100 mol%.

The polymer compound according to the present invention is more preferably a polymer compound having an acrylic skeleton and / or a styrene skeleton in the main chain, since it has a high degree of adhesion to a substrate and does not elute into an alkaline solution during plating. For example, a copolymer of polymethyl methacrylate and tetrahydropyranyl methacrylate and a copolymer of polystyrene and poly-t-butoxycarbonylmethoxystyrene have high adhesion to a substrate and excellent sensitivity. Further, the decomposition temperature of t-butyl methacrylate is as high as about 150 ° C., and the copolymer of polymethyl methacrylate and t-butyl methacrylate has excellent heat resistance. Therefore, such a copolymer is preferable when a substrate having a high glass transition temperature such as polyimide is used. Similar performance can be imparted by using acrylate instead of methacrylate.

As described above, tetrahydropyranyl methacrylate, poly-t-butoxycarbonylmethoxystyrene, and t-butyl methacrylate decompose with a small amount of acid and have high sensitivity, so that they are excellent as protecting groups for ion-exchange groups. ing. That is, in the present invention, it is preferable to have a tetrahydropyral group, a t-butyl group, and a t-butoxycarbonylmethyl group as protective groups.

In these photosensitive compositions, when a sulfonium group, a carboxyl group, or a phenolic hydroxyl group as an ion-exchange group is protected by the above-mentioned protecting group, plating nuclei are generated in the plating step. It is preferable because it is easy. That is, the polymer compound in the photosensitive composition of the present invention is a compound in which at least one selected from the group consisting of a sulfonium ester group, a carboxylic acid ester group, and a phenol derivative group is used as a repeating unit that generates an ion-exchange group. It is preferred to have.

The photosensitive composition of the present invention, even when used alone, undergoes acid decomposition to form a pattern. However,
By blending a compound having an acid-decomposable group capable of inhibiting dissolution in an alkaline solution as a dissolution inhibitor, higher sensitivity can be achieved. The dissolution inhibitor used in the present invention has a sufficient dissolution inhibiting ability in an alkaline solution, and the product after decomposition with an acid is-(C = O) OH, -S
A compound having an acid-decomposable group capable of generating (基 O) —OH or —OH is exemplified.

Such compounds include, for example, bisphenol A, bisphenol F, tri (hydroxyphenyl) methane, phenolphthalein, cresolphthalein,
Low molecular weight aromatic compounds such as thymol phthalein, catechol, pyrogallol, naphthol, bisnaphthol A, bisnaphthol F, benzoic acid derivatives and low molecular weight aliphatic alcohols such as cholates, steroids, terpenoids, saccharides, etc. It can be obtained by introducing a decomposable group.

Examples of the dissolution inhibitor include, for example, US Pat. No. 4,491,628 and US Pat. No. 4,603,101.
And the compounds described in JP-A-63-27829 and the like. Further, a compound in which part or all of the hydroxy terminal of a compound having a carboxylic acid or a phenolic hydroxyl group is substituted with an acid-decomposable protecting group can also be used as a dissolution inhibitor. For example, as the protecting group, tert-butyl ester or ter
Examples include t-butyl carbonate, a tetrahydropyranyl group, and an acetal group. As such compounds, more specifically, phenol, naphthol and anthracene, tert-butyl carbonate of polyhydroxy compound, tert-butyl carbonate of phenolphthalein and naphtholphthalein, quinazaline and quinizarin, phenol novolak and naphthol novolak resin Tert-butyl carbonate, and the like.

The addition amount of these dissolution inhibitor compounds to the polymer compound is desirably at least 3 wt% or more and less than 40 wt%. The reason is that the amount of the photosensitive composition added is 3
If the content is less than wt%, the resolution may be reduced. On the other hand, if it exceeds 40 wt%, the coating film performance or dissolution rate may be significantly reduced. More preferably, the amount of the dissolution inhibitor is usually between 10 and 30 wt%.

The photosensitive composition of the present invention is prepared by dissolving, in a solvent, a polymer compound that forms an ion-exchange group by the action of an acid and a compound that generates an acid by irradiation with actinic radiation. It is prepared by adjusting. Examples of the solvent used here include ketone solvents such as acetone, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve solvents such as methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate; ethyl acetate, butyl acetate, isoamyl acetate, and γ-solvent. Butyl lactone, and 3-
Examples include ester solvents such as methyl methoxypropionate. Further, depending on the photosensitive composition, dimethyl sulfoxide, in order to improve the solubility,
Dimethylformaldehyde, N-methylpyrrolidinone and the like may be used.

Further, propionic acid derivatives such as methyl methylpropionate, lactate esters such as ethyl lactate, which have recently attracted attention as alternative solvents to low-toxic solvents,
A solvent such as propylene glycol monomethyl ether acetate can also be used.

The abovementioned solvents can be used alone or in the form of a mixture. In addition, these solvents may contain an appropriate amount of an aliphatic alcohol such as xylene, toluene, or isopropyl alcohol.

The photosensitive composition of the present invention may contain, in addition to the above-mentioned components, a surfactant as a coating modifier, if necessary, an adhesion promoter, a basic substance, an epoxy resin; A polymer such as methyl methacrylate, polymethyl acrylate, propylene oxide-ethylene oxide copolymer, and polystyrene; or a dye as an antireflection agent may be blended.

In the present invention, since a photosensitive composition containing a photoacid generator and a compound that forms an ion-exchange group in the presence of an acid is used, a deprotection reaction of the ion-exchange group with an acid is essential. It is. For this purpose, the protecting group may be decomposed by utilizing a heat reaction by using an acid generated by a photoreaction as a catalyst. The temperature of the thermal reaction at this time must be lower than the heat resistance temperature of the insulator, and is preferably lower than the glass transition temperature in order to maintain dimensional stability. For example,
Since the glass transition temperature of PTFE is between about 100 ° C. and 130 ° C., when a PTFE film or the like is used, the temperature of the thermal reaction needs to be lower than this. Examples of the protective group that causes a deprotection reaction at a low temperature include phenolic resins such as polyhydroxystyrene and novolak resin, and t-butyl and t-butoxycarbonylmethyl groups.
Examples include those protected with valent carbon and those obtained by protecting an acrylic resin such as polymethacrylic acid or polyacrylic acid with pyranyl or lactone such as tetrahydropyranyl. Since these decompose at about 100 ° C. in the presence of an acid,
This is effective when PTFE, polystyrene, acrylic resin, and derivatives thereof having a low glass transition temperature are used as the base material.

On the other hand, when polyimide, benzocyclobutene resin, cross-linked 1,2 polybutadiene, or the like is used as the base material, the heat resistance temperature is 250 ° C. or higher, and it is up to about 400 ° C. depending on the material. Therefore, a protecting group having a high decomposition temperature can be used. In this way, a material in which a deprotection reaction does not occur unless the temperature is at least 140 ° C. even in the presence of an acid, such as a material in which an acrylic resin such as t-butyl methacrylate protected with a t-butyl group is incorporated in the copolymer composition, or the like. be able to. At this time, as the photoacid generator, an anion generated by a photoreaction such as camphorsulfonate is preferably bulky because the diffusion length is suppressed and the resolution performance is improved.

Hereinafter, each step will be described with reference to the drawings.

Step (1): First, as shown in FIG. 1 (a), a photosensitive composition layer 2 containing a compound capable of forming an ion-exchange group upon exposure is coated with a porous material of an insulator 1 made of a porous material. Formed on the surface.

Step (2): Next, as shown in FIG. 1B, the porous insulator covered with the photosensitive composition 2 formed on the insulator 1 is patterned through a mask 3. Expose. Thereby, in the exposed part 4 of the photosensitive composition 2, an acid is generated in the exposed part from the photoacid generator.

Step (3): After the exposure, a heat treatment is performed to cause the acid generated by the photoreaction to act as a catalyst to decompose the protecting group protecting the ion-exchange group in the exposed area, thereby to form an ion-exchange group. Is generated.

Step (4): Thereafter, as shown in FIG. 1C, metal ions or metals are bonded to the ion-exchange groups generated in the exposed portions 4 by the pattern exposure in the step (3).

Step (5): If necessary, as shown in FIG. 1D, a metal ion bonded to the ion-exchange group of the exposed portion 4 is subjected to a reduction treatment to metallize the metal ion, thereby providing a conductive material. Improve the performance.

Step (6): If necessary, FIG.
As shown in (e), electroless plating is applied to the conductive portion formed on the exposed portion 4 in order to improve conductivity.

When the protective group is decomposed by a thermal reaction using an acid generated from the photoacid generator upon exposure, the protective group protecting the ion-exchange group is decomposed to form the ion-exchange group. If the content is large, the metal is eluted in an alkaline plating solution or the like, and the metal is not deposited. In particular,
This phenomenon is remarkable when the ion exchange group is an acid.
Thereafter, when the protective group is heated at a temperature at which the protective group is self-decomposed by heat, the unexposed portion generates an ion-exchange group and a metal is deposited. As a result, a negative-type (metal is deposited on an unexposed portion) metal pattern is formed. At this time, two thermal reactions
It can be done in the process.

The steps (1) to (4) (optionally (5),
In (6)), complicated steps such as application, etching, and peeling of the resist are not required. Therefore, the process is simplified as compared with a conventional method of manufacturing a wiring substrate in which through holes are formed by using photolithography or a mechanical method. In addition, when a porous body is used as the insulator, there is no step of selectively plating or filling a conductive paste to form a conductive portion, and the work is facilitated.

Further, since the photosensitive composition of the present invention has high stability when not exposed, it can be stored for a long time at the stage when the photosensitive composition is immersed and coated on a substrate. For this reason, no problem occurs even if the manufacturing site that handles the photosensitive material and the manufacturing site that handles the exposure and plating are different. That is, when the photosensitive composition is dip coated on the substrate, it is shipped in the form of a product,
It is possible to easily perform pattern plating at a factory that handles plating.

Further, the precision of the pattern shape of the conductive portion can be improved, and a fine pattern controlled to several tens μm or less can be easily formed. for that reason,
The degree of freedom in designing the conductive portion formed on the insulator is also improved.

In the method for manufacturing a wiring board described in Japanese Patent Application Laid-Open No. H11-24977, it is necessary to previously form a photosensitive composition containing a metal salt on the entire surface of the insulator. On the other hand, in the present invention, such a step is not required, so that a phenomenon that metal nuclei are deposited in an undesired portion does not occur. As a result, it is possible to form a conductive portion having a fine pattern shape only in a desired portion with high accuracy.

In the present invention, since the two reactions of the deprotection group reaction and the photoreaction are separated, light having a long wavelength can be used as the exposure light. Accordingly, damage to the insulator due to exposure is reduced, and deterioration of the insulator is reduced. Further, it is possible to avoid a wavelength at which the insulator absorbs a large amount of light, and the absorption of exposure light is reduced. Therefore, it is particularly advantageous when a conductive portion penetrating in the thickness direction is formed using a porous body. In particular, when the insulator is a polymer, it is necessary to use a heat-resistant polymer for use in a wiring board. Many heat-resistant polymers have an aromatic / heterocyclic structure such as a benzene ring in a main chain or a side chain, and such an aromatic / heterocyclic structure absorbs light in an ultraviolet region. For example, a benzene ring has an absorption peak near 254 nm. For this reason, light having a short wavelength of 280 nm or less is almost absorbed, and it is difficult to perform light exposure in the film thickness direction. Further, since polyimide or the like absorbs light of 500 nm or less, it is impossible to form a through pattern by exposure to ultraviolet light.

In the present invention, a conductive portion having a fine pattern with higher precision can be formed by using, as exposure light, long-wavelength light having little absorption of an aromatic / heterocyclic structure.

In the present invention, it is desirable to use a polymer compound having at least one of a sulfonium ester group, a carboxylate ester group and a phenol derivative group as the polymer compound that forms an ion-exchange group. . The compounds listed here are versatile,
An ion-exchange group is easily generated by light irradiation. Therefore, a conductive portion having a fine pattern can be accurately formed. Further, they can be applied to any insulator, such as ceramics or organic insulating materials. Therefore, it is possible to use a low-cost insulator having high moldability.

In the method using PTFE described in JP-A-7-207450, a liquid such as water or alcohol is generally used as a compound having a hydrophilic group, and the liquid is wetted on a porous film. It is necessary to perform exposure. Therefore, there is a problem that the process and the exposure apparatus become complicated. However, according to the present invention, such a problem does not occur, and the conductive portion can be easily formed.

FIG. 2 is a schematic diagram showing an example of a multilayer wiring board using a composite board manufactured by the method of the present invention. As shown in FIG. 2, the multilayer wiring board 31
It is configured by laminating a plurality of porous films made of an insulator 34 having a conductive portion such as a wiring 2 and a wiring 33. The via 32 and the wiring 33 are formed by filling the surface or inside of the fine holes of the porous film with metal. A conductive portion 35 made of only a conductive material such as a metal is formed on an end face of such a conductive portion.

That is, in the multilayer wiring board 31 shown in FIG.
On the outermost surface of 33, there is a layer 35 made of a conductor containing no insulator component. Therefore, the resistance of the conductive portion can be reduced. Particularly in a high frequency region, the impedance characteristics can be improved by the skin effect of these structures.

The composite member manufactured by the method of the present invention can be used as a wiring substrate in a single layer without lamination. An electronic package can be obtained by electrically connecting electronic components on such a wiring board or the multilayer wiring board as described above.

[0086]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not intended to be limited to these specific examples.

Prior to the production of the composite member, a polymer compound to be blended in the photosensitive composition of the present invention was synthesized by a radical polymerization method using AIBN as an initiator. These polymers are random copolymers, and their composition ratios are shown in the following Tables 1 to 6 in mol.

[0088]

[Table 1]

In these, the first repeating unit having an ion-exchange group is t-butyl methacrylate, and the second repeating unit having an alkali-insoluble group without being decomposed into an acid is styrene. The ion-exchange group is a carboxyl group, and a t-butyl group is introduced as a protecting group.

[0090]

[Table 2]

In these, the first repeating unit having an ion-exchange group is t-butyl methacrylate, and the second repeating unit having an alkali-insoluble group without being decomposed into an acid is methyl methacrylate. The ion-exchange group is a carboxyl group, and a t-butyl group is introduced as a protecting group.

[0092]

[Table 3]

In these, the first repeating unit having an ion-exchange group is tetrahydropyranyl methacrylate, and the second repeating unit having an alkali-insoluble group without being decomposed into an acid is styrene. Also,
The ion exchange group is a carboxyl group, and a tetrahydropyranyl group is introduced as a protecting group.

[0094]

[Table 4]

In these, the first repeating unit having an ion-exchangeable group is tetrahydromethacrylate, and the second repeating unit having an alkali-insoluble group without being decomposed into an acid is methyl methacrylate. The ion-exchange group is a carboxyl group, and a tetrahydropyranyl group is introduced as a protecting group.

The molecular weight (Mw) of the above polymer compound measured by GCP was about 40,000.

[0097]

[Table 5]

In these, the first repeating unit having an ion-exchange group is t-butoxycarbonylmethoxystyrene. Hydroxystyrene is not decomposed by acids, but is soluble in alkaline solutions. Also,
The ion-exchange group is a carboxymethoxy group, and a t-butyl group or a t-butoxycarbonylmethyl group is introduced as a protecting group.

The molecular weight (Mw) of the above polymer compound measured by GCP was 10,000.

[0100]

[Table 6]

In these, the first repeating unit having an ion-exchangeable group is t-butoxycarbonylmethoxystyrene, and the second repeating unit having an alkali-insoluble group without being decomposed into an acid is styrene. . Further, the ion exchange group is a carbonyl group of a carbonylmethoxy group, and a t-butyl group is introduced as a protecting group.

Using the random copolymer obtained as described above, a pattern was formed on the insulator by the method of the present invention.

Example 1 Formation of Wiring Pattern on Porous Insulator 1 part by weight of naphthalimide / trifluoromethanesulfonate as a photoacid generator was added to each polymer compound. An acetone solution was prepared so that the total solid content of the polymer compound and the photoacid generator was 1 part by weight to prepare a photosensitive composition.

A PTFE porous film (pore diameter: 500 nm, film thickness: 20 μm) was used as an insulator, and each photosensitive composition was coated on the entire surface of the film by dipping. By this operation, the inner pore surface including the inside of the porous hole was covered with the photosensitive composition.

For this sheet, CANON PLA
Exposure was performed at 436 nm using a mask 501 having various patterns with a line width of 3 μm to 100 μm and a dot diameter of 3 μm to 100 μm to form a latent image.
Thereafter, the mixture was heated on a hot plate at 90 ° C. for 5 minutes to accelerate the deprotection reaction, thereby selectively generating an ion-exchange group in the exposed portion.

The sheet on which the pattern latent image is formed is placed on
After being immersed in a 5 M aqueous solution of copper sulfate for 5 minutes, washing with distilled water was repeated three times. Subsequently, the composite member was prepared by immersing in a 0.01M aqueous solution of sodium borohydride for 30 minutes and then washing with distilled water. In the obtained composite member, C
A conductive portion made of u was formed.

The conductive pattern forming sheet thus obtained was further immersed in an electroless copper plating solution PS-503 for 30 minutes, and the conductive portion was plated with copper to form a wiring pattern.

Tables 7 and 8 below show the polymer compounds used and the minimum dimensions of the penetrating dot patterns (vias) and line patterns (wirings) formed thereby.

[0109]

[Table 7]

[0110]

[Table 8]

A30, A50, A70, B30, B5
When 0 and B70 were used, the latent image of the pattern was visually observed during exposure and PEB, but no plating adsorption occurred. No elution of the photosensitive composition into the alkaline plating solution occurred. This is probably because the protecting group was not sufficiently decomposed.

[0112] Of C30, C50 and C70, only C30 resolved the plating pattern. C50 and C70
In, the latent image of the pattern was visually observed during the exposure and PEB, but no plating adsorption occurred. This is probably because the photosensitive composition was dissolved in the alkali.

In the D series, good plating patterns were resolved. Among these, D10 had little adhesion of plating, and it could not be said that a pattern was formed. Also D
In No. 70, the photosensitive composition was completely eluted and a pattern could not be formed. Among the patterns formed, D30 and D35 showed very good conductive performance.

In the E series, the photosensitive composition was completely eluted and a pattern could not be formed. Even in the case of E20 where a pattern was obtained, no current flowed in the conductivity test. On the other hand, in the F series, the photosensitive composition did not elute, and a good plating pattern could be obtained.

Example 2 Same as Example 1 except that the photoacid generator was changed from naphthalimide / trifluoromethanesulfonate to triphenylsulfonium / trifluoromethanesulfonate and a polymer compound of the D series was used. The photosensitive composition was prepared by the method described in the above.

The obtained photosensitive composition was applied to the same insulator as described above, and a low-pressure mercury lamp was used as an exposure light source.
Exposure was performed at an exposure amount of 0 mJ / cm ² . Thereafter, the mixture was heated on a hot plate at 90 ° C. for 5 minutes to accelerate the deprotection reaction, thereby selectively generating an ion-exchange group in the exposed portion.

Subsequently, the same processing as in Example 1 was performed to form a wiring pattern on the insulator.

The minimum dimensions of the dot pattern (via) and the line pattern (wiring) formed on the surface of the PTFE porous film as an insulator were measured. Further, the thickness of the formed dot pattern having a diameter of 50 μm in the depth direction was measured, and the obtained results are shown in Table 9 below together with the polymer compound used.

[0119]

[Table 9]

In this example, triphenylsulfonium trifluoromethanesulfonate blended as a photoacid generator is mainly exposed to a wavelength of 300 nm or less, and is considered to have been exposed to light of a low-pressure mercury lamp having a wavelength of 252 nm. At this wavelength, PTFE has poor transparency, and has a thickness of 20 μm and an absorbance of about 2. For this reason,
A plating pattern was deposited only on the exposed surface.

Further, a photosensitive composition was prepared in the same manner as described above, except that diphenyliodonium.trifluoromethanesulfonate was used as the photoacid generator. The obtained photosensitive composition was applied to the same insulator as described above, and exposed at a light exposure of 120 mJ / cm ² using a low-pressure mercury lamp as an exposure light source. After that, 90 ° C on a hot plate
To promote the deprotection reaction by heating for 5 minutes,
An ion-exchange group was selectively generated in the exposed area.

Subsequently, the same processing as in Example 1 was performed to form a wiring pattern on the insulator.

The minimum dimensions of the dot pattern (via) and the line pattern (wiring) formed on the surface of the porous PTFE film as an insulator were measured. Further, the thickness of the formed dot pattern having a diameter of 50 μm in the depth direction was measured, and the obtained results are shown in the following 10 together with the polymer compound used.

[0124]

[Table 10]

Here, diphenyliodonium trifluoromethanesulfonate blended as a photoacid generator is mainly sensitized to a wavelength of 300 nm or less, and is considered to be sensitized to light of a low-pressure mercury lamp having a wavelength of 252 nm. Therefore, a plating pattern was deposited only on the exposed surface.

The above-described method can be adopted when it is necessary to form a wiring pattern on only one side.

(Example 3) Formation of reverse pattern Naphthalimide / trifluoromethanesulfonate as a photoacid generator was added in an amount of 1 part by weight to each polymer compound. An acetone solution was prepared so that the total solid content of the polymer compound and the photoacid generator was 1 part by weight to prepare a photosensitive composition.

A PTFE porous film (pore diameter: 500 nm, film thickness: 20 μm) was used as an insulator, and each photosensitive composition was coated on the entire surface of the film by a dipping method. By this operation, the inner pore surface including the inside of the porous hole was covered with the photosensitive composition.

[0129] For this sheet, CANON PLA
Exposure was performed at 436 nm using a mask 501 having various patterns with a line width of 3 μm to 100 μm and a dot diameter of 3 μm to 100 μm to form a latent image.
Thereafter, the mixture was heated on a hot plate at 120 ° C. for 5 minutes to accelerate the deprotection reaction, thereby selectively generating an ion-exchange group in the exposed portion.

The sheet on which the pattern latent image was formed was placed
After being immersed in a 5 M aqueous solution of copper sulfate for 5 minutes, washing with distilled water was repeated three times. Subsequently, the composite member was prepared by immersing in a 0.01M aqueous solution of sodium borohydride for 30 minutes and then washing with distilled water. In the obtained composite member, C
A conductive portion made of u was formed.

The conductive pattern forming sheet thus obtained was further immersed in an electroless copper plating solution PS-503 for 30 minutes to perform copper plating on the conductive portion, thereby forming a wiring pattern.

In the wiring pattern produced in this manner, no metal pattern was deposited at a place where light was exposed, and a metal pattern was formed at a place where light was not irradiated. Table 11 below shows the patterning results.

[0133]

[Table 11]

In this embodiment, the baking temperature after exposure is controlled to control the decomposition rate of the protecting group. Thus, it can be seen that a plating pattern inverted from the positive / negative direction can be formed.

(Example 4) Formation of a wiring pattern on a polyimide film (1) Naphthalimide / trifluoromethanesulfonate was used as a photoacid generator, and one for each polymer compound.
Parts by weight were added. An acetone solution was prepared so that the total solid content of the polymer compound, the photoacid generator, and the visible light sensitizer was 1 part by weight to prepare a photosensitive composition.

As an insulator, a polyimide porous film (Upilex: manufactured by Ube Industries, pore size 500 nm, film thickness 20 μm) was used. The polyimide film used was sufficiently heated in a nitrogen atmosphere so that no amine remained. Thereafter, an oxygen plasma treatment was performed to increase the hydrophilicity.

The thus prepared insulator was coated with the respective photosensitive compositions on the entire surface of the film by dipping. By this operation, the inner pore surface including the inside of the porous hole was covered with the photosensitive composition.

[0138] For this sheet, CANON PLA
Exposure was performed using a mask 501 having various patterns with a line width of 3 μm to 100 μm and a dot diameter of 3 μm to 100 μm to form a latent image. Exposure wavelength is 550
The light of nm or less was blocked by a filter, and only visible light was used. After forming the latent image, 5 ° C. on a hot plate at 90 ° C.
By heating for a minute, the deprotection reaction was accelerated to selectively generate an ion-exchange group in the exposed area.

The sheet on which the pattern latent image is formed is placed on
After being immersed in a 5 M aqueous solution of copper sulfate for 5 minutes, washing with distilled water was repeated three times. Subsequently, the composite member was prepared by immersing in a 0.01M aqueous solution of sodium borohydride for 30 minutes and then washing with distilled water. In the obtained composite member, C
A conductive portion made of u was formed.

The conductive pattern forming sheet thus obtained was further immersed in an electroless copper plating solution PS-503 for 30 minutes, and a conductive portion was plated with copper to form a wiring pattern. Table 12 below shows the patterning results.

[0141]

[Table 12]

In the method of the present invention, an acid generated from a photoacid generator is used as a catalyst. Therefore, when a polyimide containing an amine which is a basic substance is used as an insulator, it is necessary to reduce the content of the amine as much as possible to prevent deactivation of the acid.

Example 5 Formation of Wiring Pattern on Polyimide (2) One part by weight of naphthalimide / camphorsulfonate as a photoacid generator was added to each polymer compound. An acetone solution was prepared so that the total solid content of the polymer compound, the photoacid generator, and the visible light sensitizer was 1 part by weight to prepare a photosensitive composition.

As the insulator, a polyimide porous film (upilex: manufactured by Ube Industries, pore diameter 500 nm, film thickness 20 μm) similar to that of Example 4 was used. The polyimide film used was sufficiently heated in a nitrogen atmosphere so that no amine remained. Thereafter, an oxygen plasma treatment was performed to increase the hydrophilicity.

The thus-prepared insulator was coated with the respective photosensitive compositions on the entire surface of the film by dipping. By this operation, the inner pore surface including the inside of the porous hole was covered with the photosensitive composition.

For this sheet, CANON PLA
Exposure was performed using a mask 501 having various patterns with a line width of 3 μm to 100 μm and a dot diameter of 3 μm to 100 μm to form a latent image. Exposure wavelength is 550
The light below nm was blocked by a filter and only visible light was used. After forming the latent image, 150 ° C. on a hot plate
To promote the deprotection reaction by heating for 5 minutes,
An ion-exchange group was selectively generated in the exposed area.

The sheet on which the pattern latent image is formed is placed on
After being immersed in a 5 M aqueous solution of copper sulfate for 5 minutes, washing with distilled water was repeated three times. Subsequently, the composite member was prepared by immersing in a 0.01M aqueous solution of sodium borohydride for 30 minutes and then washing with distilled water. In the obtained composite member, C
A conductive portion made of u was formed.

The conductive pattern forming sheet thus obtained was further immersed in an electroless copper plating solution PS-503 for 30 minutes, and the conductive portion was plated with copper to form a wiring pattern. Table 12 below summarizes the patterning results.

[0149]

[Table 13]

Since polyimide has high heat resistance, t-butyl methacrylate having a decomposition temperature as high as 140 ° C. or more can be used as a protective group. In order to perform post-exposure baking at a temperature as high as 150 ° C., it is necessary to use a material having a short diffusion length of an acid generated from a photoacid generator. Therefore, in this example, naphthalimide camphorsulfonate having a high anion bulk was used. As a result, a fine plating pattern could be processed into a polyimide porous film.

Example 6 Visible Light Sensitizer The same procedure as in Example 1 was carried out except that a photosensitizer (BC: Midori Kagaku) was added at a ratio of 0.3 to the weight of the photoacid generator. Similarly, a photosensitive composition was prepared.

A PTFE porous film (pore diameter: 500 nm, film thickness: 20 μm) was used as an insulator, and each photosensitive composition was coated on the entire surface of the film by a dipping method. By this operation, the inner pore surface including the inside of the porous hole was covered with the photosensitive composition.

For this sheet, CANON PLA
Exposure was performed using a mask 501 having various patterns with a line width of 3 μm to 100 μm and a dot diameter of 3 μm to 100 μm to form a latent image. Exposure wavelength is 550
The light of nm or less was blocked by a filter, and only visible light was used. After forming the latent image, 5 ° C. on a hot plate at 90 ° C.
By heating for a minute, the deprotection reaction was accelerated to selectively generate an ion-exchange group in the exposed area.

The minimum dimensions of the dot pattern (via) and the line pattern (wiring) formed on the surface of the PTFE porous film as an insulator were measured. The thickness of the formed dot pattern having a diameter of 50 μm in the depth direction was measured, and the obtained results are shown in Table 14 below together with the polymer compound used.

[0155]

[Table 14]

Although naphthalimide / trifluoromethanesulfonate is mainly insensitive at wavelengths longer than 500 nm, it is considered that it was exposed to visible light by the action of a photosensitizer. Thus, it was found that a pattern can be formed even with visible light by adding a photosensitizer.

(Example 7) Dependence on molecular weight According to the results of Example 1, the composition having the highest pattern plating performance is D35. Therefore, the ratio of tetrahydro methacrylate to methyl methacrylate is the same, and the molecular weight is different. Five polymers were polymerized. Using this, a photosensitive composition was prepared in exactly the same manner as in Example 1, and pattern plating was performed in the same manner as described above.
Table 15 below shows the weight average molecular weight Mw and patterning performance of each polymer compound.

[0158]

[Table 15]

As shown in Table 15, the molecular weight was 5000
A composition using a polymer compound of about 0 was the most excellent in resolution performance. This is because, when the composition is exactly the same, if the molecular weight is low, the solubility in the plating solution is high and elution occurs, and if the molecular weight is too high, it is difficult to maintain uniformity of wetting on the substrate surface. It is thought to be.

[0160]

As described in detail above, according to the present invention, the degree of freedom in designing a conductive circuit is high, the insulator is not deteriorated by exposure, and the fine metal is not deposited on the insulator without abnormal deposition. A method of manufacturing a composite member that can easily form a conductive portion having a pattern is provided. Further, according to the present invention, there is provided a photosensitive composition and an insulator for use in manufacturing the above-described composite member. Further, according to the present invention, there is provided a composite member manufactured by the method described above.

The present invention can be suitably used for various applications such as various optical functional devices and multilayer wiring boards, and its industrial value is enormous.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a method for manufacturing a composite member of the present invention.

FIG. 2 is a schematic view showing a multilayer wiring board including a composite member manufactured by the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Insulator 2 ... Photosensitive composition layer 3 ... Mask 4 ... Photosensitive part 5 ... Electroless plating 31 ... Multilayer wiring board 32 ... Via 33 ... Wiring 34 ... Insulator 35 ... Conductive part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/38 512 G03F 7/38 512 5G323 H01B 5/14 H01B 5/14 Z 13/00 503 13/00 503D H05K 1/03 610 H05K 1/03 610Z 3/38 3/38 A (72) Inventor Yasuyuki Hotta No. 1 Komukai Toshiba-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Pref. Toshiba R & D Center (72) Inventor Toshio Hiraoka 1 Tokoba, Komukai Toshiba-cho, Kawasaki-shi, Kanagawa F-term in the Toshiba R & D Center (Reference) 2H025 AA00 AB15 AB17 AC01 AD01 AD03 BE00 BH04 FA03 FA12 2H096 AA00 BA20 EA02 FA05 JA03 4J002 BC121 BK001 CC031 CC07001 CE EB106 EE037 EH127 EU186 EV047 EV296 EV317 EW176 GP03 5E343 AA02 AA19 AA34 AA40 BB24 DD33 DD34 EE37 ER04 FF12 FF16 GG08 5G307 GA06 GA08 GC02 5G323 CA05

Claims (8)

[Claims] 1. A method for manufacturing a composite member comprising a conductive part selectively formed on an insulator, comprising: (1) a photoacid generator;
Forming a photosensitive composition layer containing a polymer compound that generates an ion-exchange group in the presence of an acid on the insulator; and (2) pattern-exposing the photosensitive composition layer, (3) generating an ion-exchange group with an acid generated in the exposed portion of the photosensitive composition layer by the pattern exposure; and (4) forming ions by the pattern exposure. Forming a conductive portion by bonding a metal ion or metal to the pattern of the exchangeable group, wherein the polymer compound is not decomposed by an acid and a first repeating unit having an ion-exchangeable group. A method for producing a composite member, comprising: a copolymer containing a second repeating unit having an alkali-insoluble group, wherein part or all of the ion-exchange group is protected by a protective group. 2. The method of manufacturing a composite member according to claim 1, further comprising the step of: (5) performing an electroless plating on the conductive portion. 3. The method for producing a composite member according to claim 1, wherein the polymer compound has an acrylic skeleton and / or a styrene skeleton in a main chain. 4. The polymer compound according to claim 1, wherein the polymer compound has at least one group selected from the group consisting of a sulfonium ester group, a carboxylic acid ester group, and a phenol derivative group. The method for producing a composite member according to claim 1. 5. The polymer compound according to claim 1, which has a tetrahydropyral group, a t-butyl group or a t-butoxycarbonylmethyl group as a protecting group for protecting the ion-exchange group of the polymer compound. A method for manufacturing a composite member. 6. A photo-acid generator, comprising a polymer compound which forms an ion-exchange group in the presence of an acid, and a photo-sensitizer,
A photosensitive composition sensitive to light having a wavelength of 450 nm or more, wherein the polymer compound has a first repeating unit having an ion-exchange group and a second repeating unit having an alkali-insoluble group which is not decomposed into an acid. And a part or all of the ion-exchange group is protected by a protecting group. 7. An insulating material for manufacturing a composite member, wherein the insulating material has a surface of an inner hole coated with the photosensitive composition according to claim 6. Description: body. 8. A composite member manufactured by the method according to claim 1.