• 专利附录
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    • 专利摘要:
    The present invention provides an insulating film excellent in roughness and adhesion and a photosensitive resin composition and a multilayer printed circuit board capable of forming via-holes in which connection is very reliable. The present invention provides a photosensitive resin composition comprising a first resin which is an epoxy resin and a second resin having an N-substituted carbamic acid ester atom group and a radical polymerized unsaturated bond in the side chain. The second resin is preferably an oligomer having 3 to 10 repeating units represented by the following formula (1) or (3). Wherein X is H or CH 3 , Y and Z are H or an alkyl group having 1 to 4 carbon atoms, n is 0 or 1, a part of R 1 is an atomic group represented by the following Chemical Formula 2, and the remaining R 1 is Is a hydroxyl group, In the above formula, R 2 is an alkylene group having 1 to 4 carbon atoms.
    公开号:KR19980087039A
    申请号:KR1019980017352
    申请日:1998-05-14
    公开日:1998-12-05
    发明作者:마사또시 나라하라；미네오 가와모또；도끼히또 스와；마사오 스즈끼；사또루 아모；아끼오 다까하시；히로유끼 후까이；미쯔오 요꼬따；시로 고바야시；마사시 미야자끼
    申请人:우찌가사끼 이사오；히다찌 가세이 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Photosensitive resin composition and multilayer printed circuit board using the same
    The present invention relates to a photosensitive resin composition suitable for forming an optical via-hole when a multilayer circuit board is formed of an accumulation system, an insulating film obtainable by curing the composition, and a multilayer circuit board provided by the insulating film.
    Currently, printed circuit boards are being significantly improved for the purpose of reducing the size and weight of electronic devices. In particular, in order to cope with high density mounting conditions such as chips, CSP (Chip Size Package) and BGA (Ball Grid Array), the lithography in which the interlayer connection is performed through a high degree of freedom via-hole The manufacturing method of the multilayer circuit board by the accumulation system which uses the is widely used. Therefore, the high performance photosensitive resin composition which can be used for these methods is calculated | required.
    In particular, according to high-density surface mounts such as BGA and bare chip mounting, which are now widely recognized, the multilayer circuit board itself, i.e., the substrate material for mounting, is used in a mounting method such as a reflow method and a circuit coupling method. Are exposed to high temperatures. Therefore, the insulating layer should be formed of a photosensitive resin having a high glass transition point (Tg) to prevent the mounting component from deteriorating various properties such as adhesion and elastic modulus under high temperature in the mounting process and the repair process. As a photosensitive resin having a high glass transition point, a resin containing an epoxy resin as a main component, which is cured by cationic polymerization using a photoacid generator, is disclosed. For example, the technique of the photosensitive resin composition whose main component is a well-known epoxy resin is disclosed by Japanese Patent Publication No. 49-17040 (1974). Techniques mainly using epoxy resins and vinyl compounds are disclosed in Japanese Patent Laid-Open Nos. 54-48881 (1979), 56-55420 (1981), and 5-273753 (1993).
    According to the manufacturing method of the multilayer circuit board by the accumulation system using lithography as shown in Fig. 1, in general, the film of the photosensitive material (photosensitive resin composition) is provided on the core substrate 3, which is provided as the inner conductor 1 on the surface. Through holes for via hole formation which are formed on the surface of (FIG. 1 (a)), expose and develop the photosensitive film 2 through a predetermined mask, and reach the internal circuitry of the lower layer through the photosensitive layer 2 holes (Fig. 1 (b)) and the surface of the insulating layer (via through-holes for forming via-holes) to ensure adhesion to subsequently formed circuit conductors (e.g., plated copper, etc.) The inner wall) is roughened with an oxidizing agent (Fig. 1 (c-1)), and after forming a plated resist film 6 having a predetermined pattern on the roughened surface, the outer layer circuit 7 (plane Circuit and via-hole circuit) Is formed in minutes (Fig. 1 (d-1)).
    However, since the exposure amount of ultraviolet rays differs with depth by the magnetic absorption of ultraviolet rays, the degree of curing of the photosensitive resin composition varies with depth from the surface of the film upon exposure. Thus, the degree of cure is significantly different between the surface and the bottom of the film. Since the photosensitive resin composition differs in ultraviolet absorption depending on the part of the film, a significant difference occurs in exposure to the degree of curing of the top and bottom of the film. Thus, when the roughening operation of the surface is performed after the exposure and development of the film, the roughening progress at the bottom of the through-hole for forming via-holes becomes larger than the progress at the top of the film. Thus, substantially, the insulating film is peeled off and the inner diameter is expanded (i.e., at the bottom 5 of the through hole for the via-hole formation 4 as shown in Figs. 1 (c-2) and (d-2)). Problems arise, in which a reverse tapered shape is formed. The reverse tapered upper portion 5 of the through hole for via-hole formation is not preferable because it breaks the via-hole circuit and cracks occur in the insulating layer.
    In order to avoid the above problems and to uniformly match the inner wall of the through-hole for via-hole formation, it is considered to cure the insulating layer by adding a photosensitizer to the photosensitive resin composition before roughening, increasing the exposure amount and heat treatment after development. Can be. However, in this case, since the surface is not preferably roughened in the roughening process, the surface portion of the insulating film is excessively hardened, and sufficient adhesion with the planar circuit conductor cannot be obtained.
    Therefore, according to the prior art, the roughness and adhesion of the insulating film are not compatible with each other. This problem is important for insulating films whose thickness of the insulating film is 40 mu m or more. In particular, according to the prior art, via-holes larger than 25 mu m cannot be formed in the insulating film whose thickness exceeds 45 mu m.
    SUMMARY OF THE INVENTION An object of the present invention is to provide a multilayer circuit board which is provided with an insulating film having good roughness and adhesiveness, a photosensitive resin composition capable of forming a via-hole with high connection reliability, an insulating film formed of the photosensitive resin composition, and an insulating film. will be.
    1 is a schematic view showing a method of forming an insulating layer and a circuit layer using a conventional photosensitive resin composition.
    2 is a schematic view showing a method of manufacturing a multilayer circuit board of the present invention.
    3 is a schematic view showing a method of introducing an n-substituted carbamic acid ester group into the side chain of the resin.
    4 is a schematic cross-sectional view showing an example of a multilayer circuit board using the photosensitive resin composition of the present invention.
    5 is a schematic cross-sectional view showing an example of mounting an electronic device on a multilayer circuit board obtained in Example 18. FIG.
    Explanation of symbols for the main parts of the drawings
    1: internal (layer) circuit 2: photosensitive film (layer) or insulating film
    3: substrate 4: through hole or via-hole
    5: plating catalyst 6: plating resist
    7: conductor circuit layer 9: circuit board
    10: through hole 11: circuit layer
    In order to achieve the above object of the present invention, the present invention discloses a photosensitive resin composition comprising a first resin of the epoxy resin and a second resin containing an N-substituted carbamic acid ester atom group and a radical polymerized unsaturated bond in the side chain of the main component. do.
    According to the photosensitive resin composition of the present invention, even when the amount of ultraviolet irradiation decreases with the depth of the hole, the inner wall of the through-hole for forming via-holes can be uniformly cured, and the excessively hardening of the surface is crosslinked by cationic polymerization. Which can be prevented by using a combination of an epoxy resin which can be crosslinked with an N-substituted carbamic acid ester atom group which can be crosslinked by radical polymerization and a second resin having a side chain radically polymerized unsaturated bond. Therefore, according to the photosensitive resin composition of this invention, the insulating film which has a characteristic favorable in roughness and adhesiveness can be obtained. In addition, since the through hole which does not exist on the reverse taper can be formed in the insulating film, the photosensitive resin composition of the present invention is particularly suitable as a photosensitive material for forming an insulating film of a multilayer circuit board.
    Further, according to the present invention, there is provided a multilayer circuit board provided as the insulating film and the insulating film which can be obtained by curing the photosensitive resin composition and the interlayer insulating layer. Using the photosensitive resin composition of this invention, even if an insulating film is formed into a thick film, via-hole with high connection reliability can be formed in an insulating film. According to the present invention, a circuit formed on the surface of an interlayer insulating film, an interlayer insulating film having a thickness of at least 30 μm, preferably at least 45 μm, more preferably in the range of 50 to 100 μm, most preferably in the range of 50 to 60 μm. And via via interlayer insulating films, the inner diameter of which is at least 25 μm, preferably 40 to 100 μm, preferably provided as a via-hole for interlayer connection, which is present at a ratio of about 1: 1 to the thickness of the interlayer insulating film. It provides a multi-layer circuit board.
    The weight ratio of the first resin and the second resin is in the range from 0.8: 1 to 5: 1, preferably in the range from 1: 1 to 3: 1. If the second resin is small, it cannot be sufficiently prevented to form via-holes on the reverse taper. If the second resin is excessive, cationic polymerization may be hindered and the resolution may be lowered.
    The first resin of the present invention is preferably an epoxy resin having an epoxy equivalent of 100 to 500 g / equivalent. The epoxy resin used as the first resin in the present invention does not have any particular limitation, but a bifunctional resin having an epoxy equivalent of 100 to 300 g / equivalent, a trifunctional or higher polyfunctional epoxy resin having an epoxy equivalent of 160 to 500 g / equivalent, and Mixtures of these can be used. In the case of flame retardancy, halogenated epoxy resins (preferably brominated epoxy resins) can be used simultaneously.
    The bifunctional epoxy resin lowers the glaze viscosity of the photosensitive resin composition and contributes to the smoothing of the film when the photosensitive resin glaze is applied to the inner layer circuit, and imparts film plasticity to cure the photosensitive film in addition to preventing the photosensitive film from cracking after drying. After making it, the resin composition material (insulating film) is provided with adhesiveness with an internal circuit.
    According to the present invention, the bifunctional epoxy resin that can be used as the first resin is, for example, various bisphenol A epoxy resins, bisphenol F epoxy resins, aliphatic epoxy resins and alicyclic epoxy resins. Epikote 801, 802, 807, 815, 819, 825, 827, 828 and 834 (manufactured by Yuka-shell Co.), Nadecol EX-201, 212 and 821 (manufactured by Nagase Chemical Industries Co.) and KRM Epoxy resins such as 2110 and 2410 (manufactured by Asahi Denka Kogyo KK) are commercially available. Bifunctional epoxy resins having an epoxy equivalent of 300 g / equivalent or more, such as Epicoat 1001, 1004, 1009 and the like (manufactured by Yuka-shell Co.) can be used. However, when only bifunctional epoxy resin having an epoxy equivalent of 300 g / equivalent or more is used as the first resin, the glass transition point becomes too low in some cases. Therefore, the epoxy equivalent of the entire first resin is preferably adjusted in the range of 100 to 300 g / equivalent by adding the aforementioned bifunctional epoxy resin having a low epoxy equivalent.
    The trifunctional or higher trifunctional epoxy resin has the effect of increasing the glass transition point by increasing the crosslinking density of the resin composition material after curing. Trifunctional or more than trifunctional epoxy resin which can be used as 1st resin in this invention is a phenol- novolak-type epoxy resin, an orthocresol- novolak-type epoxy resin, etc., for example. Epicoats 180S65 and 1031S (manufactured by Yuka-shell Co.), ESCN-195 and 220 (manufactured by Sumitomo Chemical Co.), BREN-104, 105, EOCN-104S, EPPN-201 and 501 (manufactured by Nippon Kayaku Co.) and Trifunctional or more than trifunctional epoxy resins such as KRM-2650 (manufactured by Asahi Denka Kogyo KK) and the like are commercially available.
    As the second resin in the present invention, a resin containing an N-substituted carbamic acid ester atom group and a radical polymerized unsaturated bond in the side chain of the main component is used. As the radical polymerization unsaturated bond, vinyl ester atom groups are preferable. Resins having vinyl ester atom groups in the side chain are disclosed in Nihon Secchaku Gakkaishi, J. of Japanese Society of Adhesion, vol. 31, No. 8, p334 (1995).
    The main chain skeleton of the second resin is not particularly limited, and the second resin may be formed in accordance with the required membrane properties only if the resin can form an N-substituted carbamic acid ester atom group (preferably having a hydroxyl group) in its side chain. , May be arbitrarily selected from any resin. However, with respect to the glass transition point (Tg), polyfunctional epoxy resins such as various bisphenol A epoxy resins, bisphenol F epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, phenol novolak type epoxy resins and orthocresol novolak type resins, and the like Halides of these resins, such as bromide, are preferred as the main chain. In particular, since the radically polymerized vinyl group is introduced into the side chain thereof, a polyfunctional epoxy resin to which acrylic acid or methacrylic acid is added is preferable. Thus, resins in which the hydroxyl group of an epoxy acrylate resin or epoxy methacrylate resin is partially substituted with an N-substituted carbamic acid ester atom group are particularly suitable as the second resin.
    In order to introduce an N-substituted carbamic acid ester atom group into the side chain of these main chain compounds, for example, as shown in Fig. 3, the main chain compound A having a hydroxyl group is used, and the compound B having an isocyanate group is used as the hydroxide of the main chain compound A. Add to part of the siloxane group.
    Since radically polymerized vinyl groups can be introduced, it is preferable to use acrylic isocyanate or methacryl isocyanate as the compound having isocyanate. Therefore, isocyanate addition epoxy acrylate resin or isocyanurate addition epoxy methacrylate resin is especially preferable as a 2nd resin.
    Substantially, halides of oligomers or oligomers represented by the following general formula (1), or halides of oligomers or oligomers represented by the following general formula (3) are preferably used as the second resin.
    Formula 1
    Formula 3
    Where
    X is hydrogen or a methyl group,
    Y is hydrogen or an alkyl group having 1 to 4 carbon atoms,
    n is 0 or 1,
    Two Xs bonded to a carbon atom may be the same or different from each other.
    In Formula 1 and Formula 3, some of R 1 included in the molecule are N-substituted carbamic acid ester atom groups represented by the following Formula 2, and the remaining R 1 is a hydroxyl group.
    Formula 2
    Where
    R 2 is an alkylene group having 1 to 4 carbon atoms,
    Z is hydrogen or an alkyl group having 1 to 4 carbon atoms.
    The proportion of N-substituted carbamic acid ester atoms that occupy the total number of R 1 in the molecule is preferably at least 0.5 mol%, preferably less than 20 mol% to maintain sufficient resolution to obtain a sufficient effect. As the halide, for example, an aromatic nucleus in which at least one hydrogen is substituted with a halogen atom can be used.
    The resin composition of the present invention also preferably contains a substance which generates an acid and / or a radical by light irradiation, that is, a photoacid generator and / or a radical photopolymerization initiator.
    The photo acid generator is a component which generates an acid by light irradiation and contributes to curing the epoxy resin by cationic polymerization, and its content is preferably 1 to 10 weight based on 100 parts by weight of the total weight of the first and second resins. It is a range of wealth. However, when the photo acid generator is present in excess of 1 part by weight, sufficient resolution can be obtained. When the photoacid generator is present in less than 10 parts by weight, sufficient roughness can be maintained.
    The radical photopolymerization initiator is a component that generates radical species by light irradiation and contributes to curing the resin having a vinyl group capable of radical polymerization by radical polymerization, and the content thereof is preferably the first and second resins. It is the range of 0.1-5 weight part with respect to 100 weight part of total weight. However, when the initiator is present in excess of 0.1 parts by weight, sufficient effect can be obtained to prevent the formation of the reverse tapered phase. If the initiator is present in less than 5 parts by weight, sufficient resolution can be maintained.
    The present invention can be carried out without using a radical photopolymerization initiator when the photoacid generator generates radicals by light irradiation. However, in order to obtain a high effect, it is preferable to add a radical photopolymerization initiator.
    Suitable photoacid generators for the present invention are sulfonium salts and iodonium salts and the like, and the counter anions thereof are BF 4 , PF 6 , AsF 6 and SbF 6 .
    Examples of sulfonium salts include triphenyl sulfonium salt, dimethylphenyl sulfonium salt, diphenylbenzyl sulfonium salt, tritolylphenyl sulfonium salt, 4-butoxyphenyl diphenyl sulfonium salt, tris (4-phenoxyphenyl) sulfonium salt, 4- Acetoxy-phenyl diphenyl sulfonium salt, tris (4-thiomethoxyphenyl) sulfonium salt, di (methoxynaphthyl) methyl sulfonium salt, dimethylnaphthyl sulfonium salt and phenylmethyl benzyl sulfonium salt. Examples of iodonium salts include diphenyl iodonium salts, phenyl-2-thienyl iodonium salts, di (2,4-methoxyphenyl) iodonium salts, di (3-methoxycarbonylphenyl) iodonium salts, Di (4-acetoamidophenyl) iodonium salt and (4-octyloxyphenyl) phenyl iodonium salt.
    Suitable photoradical polymerization initiators for the present invention are carbonyl compounds represented by benzoin, polynuclear quinoline, for example methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amyl An azo compound represented by azobisisobutyronitrile, such as anthraquinone, and a diazonium compound, mercaptans, the organosulfur compound represented by alkyl disulfide, alkyl metals, metal carbonyls, and other various compounds. In particular, a carbonyl compound is preferable.
    Among the radical polymerization initiators of the carbonyl compound, there are two types, for example, hydrogen attracted and self cleaved. Hydrogen attracted compounds include thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone and 2-methylthioxanthone, 2 And 4-diisopropyl thioxanthone and the like and benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone. Although the said hydrogen attracting initiator can be used, a self-cleaving radical polymerization initiator is suitable for this invention.
    Self cleaving radical polymerization initiators such as benzoin and alkyl ethers thereof, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl methyl ketal, Phenones such as acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, diethoxy acetophenone, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 1-hydroxycyclohexyl phenyl ketone, and the like, and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal.
    In order to accelerate the rate of cure, a polymerization accelerator may be used. Polymerization promoters are, for example, ethanol amines, tertiary amines such as N-methyl diethanol amines, benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and 4-dimethylaminobenzoic acid ethyl ether and the like. The amount of these amine group polymerization promoters to be used is adjusted so as not to interfere with cationic polymerization.
    The photosensitive resin composition of this invention preferably further contains the 3rd resin which has a phenol hydroxyl group. By adding a third resin, it is possible to increase the solubility into developing aqueous solution (especially alkaline aqueous solution) during development and to increase the glass transition point (Tg) of the resin composition material after curing, which means that the third resin is epoxy during curing. This is because it reacts with the resin to increase the crosslinking density.
    The resin having a phenolic hydroxyl group that can be used as the third resin in the present invention is, for example, a polyhydric styrene such as a novolak resin, a resol resin, a hydroxy styrene polymer, or a polyhydride such as a hydroxyphenylmaleimide polymer. Oxyphenylmaleimide and the like. In particular, various resol resins having both a phenolic hydroxyl group and a methylol group in the molecule are preferable. Resins with self-condensed phenolic hydroxyl groups, such as resol resins, cause self-condensation reactions with acid catalysts, increase the crosslinking density upon curing, provide a cured film with a high glass transition point, and provide a cured film with residual phenolic hydroxyl groups in the cured film. By reducing the amount, the plating solution resistance is improved.
    As a 3rd resin, the novolak resin which is a condensation product of the compound which has a phenol hydroxyl group, and formaldehyde is preferable. In the present invention, such as o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol Compounds with phenolic hydroxyl groups and mixtures thereof and condensation products of formaldehyde are suitable, and m, p-cresol novolak phenol is particularly preferred.
    When using the third resin, a content of 5 parts by weight or more of the third resin relative to 100 parts by weight of the first and second resins is sufficient to maintain its advantage, and when the content is less than 30 parts by weight, the desired solubility in the developer is determined. I can keep it.
    Moreover, the photosensitive resin composition of this invention contains a rubber component preferably. By adding the rubber component, the resin composition film after curing obtains plasticity, prevents the film from cracking, and increases its adhesion with the conductor circuit.
    The rubber component which can be used in the present invention is, for example, a copolymer of acrylonitrile-butadiene having a polybutadiene and its epoxy compound, a vinyl group, an amino group or a carboxyl group at its terminal, a copolymer of these resins with an epoxy resin, and the like. . In particular, rubber modified with an epoxy resin is preferable. These resins can be used alone or in combination of two or more thereof.
    In the case of using the rubber component, a content in the range of 5 to 40 parts by weight of the rubber component is preferable with respect to 100 parts by weight of the total weight of the first and second resins. And good adhesion contact with the plated circuit. When the rubber component is added in excess of 40 parts by weight, the resolution is deteriorated, and the glass transition point of the resin composition film after curing is lowered.
    Further, the photosensitive resin composition of the present invention preferably contains fine particles of rubber. By disperse | distributing the fine particle of rubber | gum in a film | membrane, it can suppress that the glass transition point of a hardened film | membrane falls. The particle size of the fine particles of rubber is preferably smaller than the film thickness of the formed insulating film and the diameter of the via-holes. For example, XR 91P (manufactured by Japan Synthetic Rubber Co.) and YR-528 and YR-516 (manufactured by Tohto Kasei Co.) in which rubber particles are dispersed in an epoxy resin are suitable for the present invention. A content in the range of 5 to 20 parts by weight of fine particles of rubber is preferred for 100 parts by weight of the total weight of the first, second and third resins.
    Moreover, the photosensitive resin composition of this invention can contain a radical curable 4th resin. Radical curable resins are resins having radically curable unsaturated double bonds, for example reactive monomers of styrene, acrylic acid and methacrylic acid, polyfunctional oligomers and the raw materials of the aforementioned second resins, i.e., N-substituted carbamic acid ester atoms in the side chains. It may be a resin having a vinyl ester atom group in the side chain before introducing. In particular, a resin having a vinyl ester atom group in the side chain in which carboxylic acid anhydride is added to the hydroxyl group of the side chain is preferable because solubility in a developing solution can be improved.
    When using the fourth resin, the content in the range of 5 to 30 parts by weight of the fourth resin is preferred relative to 100 parts by weight of the total weight of the first, second and third resins. The fourth resin may be polymerized by the above-mentioned radical photopolymerization initiator.
    Moreover, in order to improve resin properties / film properties, the photosensitive resin composition of the present invention may suitably contain a thermosetting agent, a releasing agent, a flame retardant, a photosensitizer, inorganic compound particles, an equalizer, and the like. By using these reagents, heat resistance, roughness, plating resistance, developability, tack free and antimicrobial heat resistance can be improved.
    The thermosetting agent is a thermosetting catalyst for epoxy resins, and the residual epoxy resin can be cured by heating after the photo curing reaction. When using a thermal curing agent, the crosslinking density of the resin composition material after the photocuring may be increased to be greater than the crosslinking density of the resin composition material which is cured only by the photoacid generator during photocuring and / or by heat treatment after photocuring. And increase the glass transition point.
    The thermosetting agent suitable for this invention is various thermosetting catalysts for epoxy resins, for example, triphenylphosphine, imidazole, etc. In particular, the thermosensitive onium salt which generates an acid when heated is preferable. For example, 2-butenyltetramethylenesulfonium hexafluoroantimonate (CP-66) (manufactured by Asahi Denka Kogyo K.K.) and the like can be used commercially. When using a thermosetting agent, the kind and content thereof can be adjusted according to properties such as the glass transition point and the elastic modulus required for the resin composition after curing.
    When using a compound selected from triphenylphosphine-based or imidazole-based as a heat curing agent, the content of the heat curing agent is preferably added to 100 parts by weight of the first to fourth resins described above in order not to inhibit the light curing reaction. 1 part by weight or less. When the onium salt is used, since the onium salt does not inhibit the photocuring reaction, the content may increase by more than 1 part by weight relative to 100 parts by weight of the total weight of the first to fourth resins described above. However, in order to avoid breaking the resin composition film after curing, the content is preferably limited to less than 10 parts by weight.
    A release agent is a reagent for coating the surface of the photoresist film by dropping it out of the surface of the photoresist film during drying and curing. By coating the surface, the dryness of the photosensitive film can be improved, and the developability can be improved by exposing the impregnation of the developer and suppressing it to the cured portion. Suitable release agents for the present invention are, for example, polysiloxanes, polyethers and polymers thereof, and these reagents may be used alone or in combination. Examples of the siloxane include dimethyl polysiloxanes modified with methyl styrene, long chain alkyl, polyether, carbinol, epoxy, carboxyl, such as straight silicone oil, such as dimethyl silicone oil, methylphenylsilicone oil and methylhydrogen silicone oil. , Mercapto, higher fatty acids and methacryl. Commercially available are Perenol F40 and Perenol S43 (manufactured by Sun Nopuco Co.), SC5570 (manufactured by Toray-dow Corning Silicone Co.) and TSA 750 (manufactured by Toshiba silicone Co.). In the case of using a release agent, the content of the release agent is preferably in the range of 1 to 5 parts by weight based on 100 parts by weight of the first to fourth resins described above.
    The flame retardant is a component that contributes to flame retardation of the photosensitive resin composition, and a material known as a flame retardant or a flame retardant aid can be used. Flame retardants suitable for the present invention are, for example, halides of epoxy, aromatic, aliphatic and cycloaliphatic compounds, red phosphorus or white phosphorus, phosphorus compounds such as non-halogenated phosphorus esters, halogenated phosphorus esters, polyphosphates, poly Phosphates, polyol-containing phosphorus, polyphosphoric acid and the like and antimony-based flame retardants such as antimony trioxide and the like. Moreover, two or more kinds of flame retardants optionally selected from the above flame retardants may be used simultaneously to take advantage of their synergistic effects. When using a flame retardant, the content of the flame retardant is preferably in the range of 1 to 10 parts by weight, particularly 3 to 10 parts by weight, relative to 100 parts by weight of the first to fourth resins described above. When the content of the flame retardant is very small, a sufficient flame retardant effect is not obtained, and when the content is very large, the flame retardant has a weak effect on the resolution, adhesion, and plating solution contamination.
    As the photosensitizer, any compound which acts to sense the photoacid generator can be widely used. For example, photosensitizers that act as photosensitizers for sulfonium salts are derivatives such as perylene, anthracene and phenothiazine. Photoresists that act as photosensitizers for iodonium salts are dyes such as acridine orange, acridine yellow, benzoflavin, phosphine R and cetoflavin T and the like. SP 110 (manufactured by Asahi Denka Kogyo K.K.) is commercially available. When using a photosensitizer, the content of the photosensitizer is preferably in the range of 0.1 to 5 parts by weight relative to 100 parts by weight of the total weight of the first to fourth resins described above.
    The inorganic compound particles have the effect of increasing the dryness of the photosensitive film and improving the surface roughening efficiency of the plated film of the resin composition material after curing, and may use hydroxides, oxides or carbonates of elements in group IIa IIIa or IVa. Any one of these materials may be used, or two or more selected from these materials may be used simultaneously. The inorganic compound particles which can be used in the present invention are, for example, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, silicon oxide and the like. The particle size of the inorganic compound is preferably smaller than the thickness of the insulating film to be formed and the diameter of the via-hole.
    In the case of using the inorganic compound particles, the content of the particles is preferably in the range of 3 to 50 parts by weight relative to 100 parts by weight of the first to fourth resins described above. When the content exceeds 3 parts by weight, a sufficient effect for improving the adhesion can be obtained, but when the content exceeds 50 parts by weight, the developability is impaired.
    The equalizer is an additive for improving the flatness of the photosensitive film after forming (printing) the film, and an acrylic ester copolymer may be used. Commercially available equalizers are, for example, Modaflow (manufactured by Mont Santo Co.). When using an equalizer, the content of the reagent is preferably in the range of 0.5 to 10 parts by weight relative to 100 parts by weight of the total weight of the first to fourth resins described above.
    The photosensitive resin composition of this invention can contain a solvent arbitrarily. That is, the photosensitive resin glaze obtained by dissolving or dispersing components selected from the above reactive components in a solvent is also preferable as the photosensitive resin composition of the present invention.
    In the resin composition of the present invention, solvents such as aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol and ethanol, esters such as ethyl acetate and butyl acetate, ketones such as methylethyl ketone and tetrahydrofuran, ethylene glycol Glycol ethers such as monomethyl ether and ethylene glycol monoethyl ether, glycol derivatives such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and diethylene glycol monomethyl ether acetate, cyclohexanone and cyclohexanol Alicyclic hydrocarbons such as and the like, and petroleum solvents such as petroleum ether and petroleum naphtha.
    The solid concentration of the photosensitive resin composition of this invention in a glaze can be arbitrarily determined according to the film formation method, the film thickness after film formation, etc. However, since a film having a film thickness generally in the range of 20 to 100 m can be formed by only one application, a content in the range of 30 to 80% by weight is preferable.
    The above and other objects, features and advantages of the present invention are more clearly understood in the following detailed description with reference to the drawings.
    Examples 1-9
    Glazes having a solid concentration of 60% by weight were prepared by dissolving or dispersing each component shown in Table 1 in 1-acetoxy-2-ethoxyethane, and their performance was evaluated by performing the following tests 1 to 7. The results of the test were all preferred as shown in Table 1. That is, in all of Examples 1-9, the resin film which has favorable adhesiveness, the periphery of the through-hole for via-hole formation, does not peel, and has favorable characteristics was obtained. The resin film had suitable properties for the high resolution, high glass transition point and the insulating film of the multilayer circuit board.
    Example One23456 Ep-828 * 1 5.655555 ESCN-195 * 1 ----45- BREN-105 * 1 -----45 KRM-2650 * 1 50454545-- CNA * 1 44.44040404040 HP-180R * 1 -1010101010 UV1-6974 * 2 333333 XER91P * 2 ------ DT-8208 * 2 --10101010 R5259 * 2 ------ CP66 * 2 --3333 SP100 * 2 ---0.30.30.3 S43 * 2 --OneOneOneOne Silicon Oxide * 2 --13131313 Film thickness (㎛)525255535555 Dry touchOOOOOO Resolution (μm)252540404040 Tg (℃)190220210210205215 Adhesive * 3 0.70.70.90.91.00.8 Adhesive * 4 0.80.91.01.11.21.2 Peel * 5 OOOOOO Indications: * 1: Part * 2: Part to 100 parts total weight of the compound indicated by * 1 * 3: Adhesiveness of the inner layer circuit * 4: Adhesiveness of the plated circuit * 5: Peeling at the bottom of the via-hole
    ExampleComparative example 789One23 Ep-828 * 1 6.31058.38.38.3 ESCN-195 * 1 ------ BREN-105 * 1 ------ KRM-2650 * 1 56.224045757575 CNA105 * 1 54040--- HP-180R * 1 12.5101016.716.716.7 UV1-6974 * 2 3.833555 XER91P * 2 --5--- DT-8208 * 2 12.5101016.7616.7616.76 R5259 * 2 25--6.76.76.75 CP66 * 2 3.83355- SP100 * 2 0.40.30.3--0.5 S43 * 2 1.3OneOne1.71.71.7 Silicon Oxide * 2 16.3131321.7521.7521.75 Film thickness (㎛)535553333 Dry touchOOOOOO Resolution (μm)404040404040 Tg (℃)218210220210210210 Adhesive * 3 0.90.90.90.90.90.9 Adhesive * 4 1.41.41.41.40.30.3 Peel * 5 OOOOOO Indications: * 1: Part * 2: Part to 100 parts total weight of the compound indicated by * 1 * 3: Adhesiveness of the inner layer circuit * 4: Adhesiveness of the plated circuit * 5: Peeling at the bottom of the via-hole
    The first resin consisted of a polyfunctional epoxy resin, Ep-828 is a bisphenol A epoxy resin (189 g / equivalent, manufactured by Yuka-Shell Co.), and ESCN-195 is a cresol novolak type epoxy resin (198 g / equivalent , Manufactured by Sumitomo Chemical Co.), BREN-105 is a brominated novolac epoxy resin (270 g / equivalent, manufactured by Nippon Kayaku Co.), and KRM-2650 is a cresol novolac epoxy resin (220 g / equivalent, Asahi Denka Kogyo KK). The second resin having an N-substituted carbamic acid ester atom group and a radical polymerization unsaturated bond is CNA105 (manufactured by Nippon Kayaku Co.), which is an epoxy acrylate (acrylic isocyanate addition rate is 2%) with acryl isocyanate added, and a phenolic hydroxyl group The third resin having was HP-180R (manufactured by Hitachi Chemical Co.) which is a resole resin.
    UVI-6974 is triphenylsulfonium hexafluoroantimonate (photoacid generator) (manufactured by Union Carbide Co.), XER91P (manufactured by Daito Sangyo Co.) is a rubber fine particle, DT-8208 (Daito Sangyo Co.) ) Is epoxy modified rubber, R5259 (radical polymerized resin) (manufactured by Nippon Kayaku Co.) is epoxy acrylate (acid value KOH 72 mg / mg) with acid anhydride added, CP-66 (Asahi Denka Kogyo KK Manufactured) is 2-butenyl tetramethylene-sulfonium hexafluoroantimonate (thermal curing agent), SP100 (manufactured by Asahi Denka Kogyo KK) is a photosensitizer for UVI-6974, and S43 is a polysiloxane copolymer (release agent) Perenol S43 (manufactured by Sun Nobuco Co.), and the silicon oxide fine particles used had an average particle size of 1 m.
    (1) evaluation of resolution (development)
    The photosensitive glaze was applied onto a copper surface of a metal foil having a dual structure of aluminum and copper (UTC foil, manufactured by Mitsui Mining Smelting Co., thickness: 50 μm), and the applied glaze was applied at room temperature for 1 hour and at 120 ° C. for 15 hours. Drying for minutes gave a sample with a photosensitive layer. Specimens were irradiated with ultraviolet light of 2.5 J / cm 2 with ultra-high pressure mercury lamps through via-hole masks with diameters ranging from 10 to 160 μm. The curing of the photosensitive layer was then enhanced by heating at 120 ° C. for 15 minutes, after which the photosensitive layer was charged with an aqueous solution containing 400 ml / l of 2,2-butoxyethoxyethanol and 10 g / l of sodium hydroxide. It was developed by spraying on the layer.
    The resolution was determined by the minimum diameter of the via-hole that could be developed (ie the smallest inner diameter of the through hole obtained).
    (2) Evaluation of contact dryness
    If the photo-sensitive layer adhered to the via-hole mask when the via-hole mask was peeled off from the exposed specimen during the resolution test, the sample was determined to be poorly dry and the sample not attached to the mask was determined to be good. In Table 1, poor touch-drying is represented by x, and good touch-drying is represented by ○.
    (3) determination of film thickness
    The developed sample obtained by the test for evaluation of the resolution (1) above was cured by heating at 180 ° C. for 2 hours. Subsequently, the aluminum layer was etched with an aqueous sodium hydroxide solution, washed, and then cured again by etching the copper layer with an etchant consisting of a mixture of sulfuric acid (100 g / l) and 35% aqueous hydrogen peroxide solution (200 g / l). The cured film was separated from the foil and the thickness of the film was measured.
    (4) determination of glass transition temperature
    Samples were prepared by cutting the cured film used to determine the film thickness into a 30 mm x 5 mm rectangle, and the glass transition temperature was determined by measuring the mechanical viscoelasticity using an instrument (manufactured by IT Measurement and Control Co.). . The measurement conditions were distance between support points: 20 mm, measurement frequency: 10 Hz, temperature increase rate: 5 ° C./min, measurement temperature range: room temperature to 300 ° C.
    (5) Determination of adhesive force with inner layer circuit
    After the surface of 20 micrometer-thick copper foil was roughened with the ammonium persulfate aqueous solution, the oxide layer was formed into the aqueous solution containing sodium perchlorate as a main component. The oxide layer was reduced by treatment with an aqueous dimethylamine borane solution and dried. The photosensitive glaze was applied to the roughened surface obtained, dried, exposed to the same entire surface as the test of (1) resolution evaluation above, and cured by heating at 180 ° C. for 2 hours. Subsequently, a resin film was applied to the glass epoxy substrate by applying an epoxy adhesive (Araldite, manufactured by Nagase-Chiba Co.) to the surface of the resin film. Peel strength of the copper foil was measured by the method defined in JIS C6481.
    (6) Determination of adhesive force with plated circuits
    A copper plated laminate having an 18 μm thick copper foil was treated on the surface of the copper foil, coated with a photosensitive glaze, exposed to form a resin film, heated at 140 ° C. for 30 minutes to enhance curing, and the surface to an aqueous solution of permanganic acid. The treatment was carried out in the same manner as in the above test (5) by roughening, treating to neutralize, adding a plating catalyst, and treating for activation. However, only Comparative Example 2 was heated at 180 ° C. for 60 minutes to enhance curing. Then, a copper layer was formed on the surface of the resin film activated by chemical plating, and then a panel plated copper layer of about 20 탆 thickness was formed by electroplating. The layer was further heated at 180 ° C. for 2 hours, then the peel strength of the plated copper layer was measured by the method defined in JIS C6481.
    (7) Confirmation of Via-Hole Stripping After Harmonic Treatment
    A copper plated laminate having an 18 μm thick copper foil was treated on the surface of the copper foil, coated with a photosensitive glaze, and exposed through the same via-hole mask as in the above test (1) to penetrate the resin film to the low layer copper foil. A through hole reached was formed, heated to enhance hardening, and then treated in the same manner as in Test (5) by the step of roughening the surface in the same manner as in (5). Next, the through hole was observed around. However, when the same harmonic conditions were used, the results changed slightly depending on the diameter of the via-hole. Therefore, via-holes of 50 μm in diameter were observed in all examples and comparative examples. In the case where no peeling was observed at the bottom of the hole through the resin film, it was expressed as ○ in Table 1, and in the case where any peeling occurred and whitening was observed at the bottom of the through hole, it was expressed as × in Table 1, respectively.
    Comparative Examples 1 to 3
    According to Comparative Example 1, a photosensitive resin composition containing no N-substituted carbamic acid ester atom group and a resin having a radically polymerized unsaturated bond in the side chain (CNA105) was used to form a resin film in the same manner as in Examples 1-9. However, delamination occurred at the bottom of the hole through the resin film, which formed a reverse tapered phase.
    The film of Comparative Example 2 was formed in the same manner as in Comparative Example 1 except that the curing was strengthened by heating at 180 ° C. for 2 hours before roughening. According to Comparative Example 2, no peeling at the bottom of the hole through the membrane occurred during the roughening treatment due to the effect of the thermosetting agent. However, the film was not practical because the surface of the resin film was not well matched and the adhesiveness of the resin film having the plated copper layer was weak.
    The film of Comparative Example 3 was formed in the same manner as in Comparative Example 1 except that the photosensitive agent was added to the photosensitive glaze. According to Comparative Example 3, no peeling at the bottom of the hole through the membrane occurred during the roughening treatment as in Comparative Example 2. However, the film was not practical because the surface of the resin film was not well matched and the adhesiveness of the resin film having the plated copper layer was weak.
    Example 10
    Internal circuit boards were prepared by etching a glass epoxy substrate having a 18 μm thick copper layer. The surface of the inner layer circuit board was roughened with an aqueous ammonium persulfate solution, and an oxide film was formed with an aqueous sodium perchlorate solution. Subsequently, the oxide layer was treated with an aqueous dimethylamine borane solution to reduce and dry. Subsequently, the photosensitive glaze of Example 4 was applied by screen printing to the treated internal circuit surface to form a photosensitive layer and dried. The thickness of the photosensitive layer was about 50 μm.
    Subsequently, in a predetermined portion, an insulating film provided as a through-hole for forming via-holes penetrating through the insulating film and reaching a lower layer circuit was irradiated to a predetermined position through a via-hole mask (2.5 J / cm 2), Example 1 It was obtained by heating for 30 minutes at 140 ℃ the same as in the 9-9.
    After mechanically polishing the surface of the obtained insulating film, the inner wall of the through-hole for via-hole formation and the surface of the insulating film were roughened with an aqueous solution of permanganic acid. Subsequently, after neutralizing and adding a plating catalyst, a pattern was formed by laminating etching resists. The plating catalyst could then be activated and the conductors precipitated by chemical plating on the activated surface to form the microcircuits of the via-holes and the second layer. After drying, postcure was carried out at 180 ° C. for 2 hours.
    Furthermore, as shown in Fig. 2E, the multilayer circuit board was obtained by forming the multilayer by repeating each process of the same photosensitive film formation, surface treatment and conductor formation. The obtained substrate 9 was impregnated in a solder reflow vessel at 200 ° C. for 10 minutes and impregnated in a solder reflow machine at 288 ° C. for 1 minute, but any peeling was observed between the conductor circuit and the photosensitive layers. It wasn't.
    As a result of this Example, the heat-resistant photosensitive resin composition of this Example was able to be developed with a non-flammable developing aqueous solution, and had high adhesiveness with the conductor circuit while suppressing the high touch-drying property and the reduction of the glass transition point without lowering its resolution. According to this Example, the excellent heat resistance high density multilayer circuit board was obtained using the photosensitive resin composition which has the outstanding characteristic.
    Examples 11-16
    The surface of the copper layer was roughened with an aqueous ammonium persulfate solution using a glass epoxy substrate having a copper layer having a thickness of 18 μm, the oxide film was formed into an aqueous solution containing sodium perchlorate as a main component, and reduced with an aqueous dimethylamine borane solution, An internal circuit board was prepared by the drying step. Subsequently, the photosensitive glaze was obtained by dissolving and dispersing each component as diethylene glycol monomethylether acetate having a solid concentration of 70% by weight and as shown in Table 2, which was screen printed onto a substrate, and dried.
    Subsequently, in order to form via-holes of various sizes, the substrate was irradiated with a high-pressure mercury lamp through a via-hole mask at a predetermined position (2.7 J / cm 2) and heated at 120 ° C. for 15 minutes to enhance its curing. . The thickness of the obtained resin film was measured. The results are shown in Table 2.
    Subsequently, the membrane was developed by spray development with a development compliance solution (400 ml / l of 2,2-butoxyethoxyethanol and 10 g / l sodium hydroxide). The diameter of the via-hole that can be developed at the same time (ie, the inner diameter of the smallest of the obtained through holes) was determined as the resolution.
    Subsequently, heating at 150 ° C. for 1 hour enhances curing, the surface is treated with an aqueous solution of permanganic acid, neutralized, a plating catalyst is added, treated for activation, and a panel plating about 20 μm thick is obtained in Example 1 In the same manner as in the ninth to ninth embodiment, the substrate was plated using chemical plating and electroplating at the same time, and heated at 180 ° C. for 2 hours to prepare a substrate provided as a through-hole for forming via-holes having an insulating film.
    The through hole part (100 micrometers in diameter) of the obtained board | substrate was cut | disconnected by the low speed cutter, the cross section was ground, and it observed and evaluated. The results are also shown in Table 2. In Table 2, the via-hole shape is expressed as ○ when the reverse reduction portion inside the via-hole is not observed in any 100 samples (cross section of the through hole) and a uniform plating film is formed, and the reverse reduction inside the via-hole Although a part is observed, it is represented by (triangle | delta) when the plating film is formed uniformly and a board | substrate is substantially usable, and x when the reverse reduction part generate | occur | produces inside a via-hole and a plating film was formed nonuniformly.
    Adhesion and soldering heat resistance with the plated circuits shown in Table 2 were measured according to the method defined in JIS C6481. Soldering heat resistance was measured at 260 ° C.
    Example 111213141516 KRM-2650 * 1 454545454545 Ep-828 * 1 555555 CNA117 * 1 303030303030 SP-70 * 1 333333 RPI * 2 () * 1 I-184 (0.1)I-184 (0.5)I-184 (1.0)I-651 (0.5)I-1173 (0.5)DETX-S (0.5) HP180R * 1 101010101010 DT8208 * 1 151515151515 CP66 * 1 333333 SP100 * 1 0.30.30.30.30.30.3 R5259 * 1 101010101010 SiO 2 * 1 151515151515 Film thickness * 3 535959575858 Resolution * 3 607080708090 Via-Hole Shape△○○○○△ Adhesion * 4 1.200.951.051.001.100.90 Soldering Heat Resistance * 5 606060606040 * 1: parts by weight * 2: radical polymerization initiator * 3: 占 퐉 * 4: adhesive strength with plated wiring (kgf / cm) * 5: soldering heat resistance (second)
    According to the said result, it was confirmed that the photosensitive resin composition used by Examples 11-16 and the multilayer circuit board obtained by this are a preferable product with high connection reliability. Moreover, the heat resistance expressed by the soldering heat resistance was found to be improved by increasing the internal curing property.
    In particular, according to Examples 12-15 using self cleavable radical polymerization initiators, it was possible to form through holes with clearly good shapes (ie without reverse tapered ripples). Example 11 showed that although the amount of radical photopolymerization initiator was small, the via-hole shape and the soldering heat resistance were observed to be improved.
    In Table 2, CNA-117 is epoxy acrylate (2% acryl isocyanate content) added to acrylic isocyanurate (manufactured by Nippon Kayaku Co.), HP-180R is resol resin (manufactured by Hitachi Chemical Co.), SP-70 is triphenylsulfonium hexafluoroantimonate (photoacid generator) (manufactured by Asahi Denka Kogyo KK), and I-184 is 1-hydroxycyclohexyl phenylketone (self cleaving radical polymerization initiator) ( Ciba-Geigy Co.), I-651 is benzyldimethyl ketal (self cleaving radical polymerization initiator) (manufactured by Ciba-Geigy Co.), and I-1173 is 2-hydroxy-2-methyl-1-phenyl Propane-1-one (self cleavable radical polymerization initiator) (manufactured by Ciba-Geigy Co.), DETX-S is Kayakure DETX-S (manufactured by Nippon Kayaku Co.), ie 2,4-diethyl Thioxanthone (hydrogen drag type polymerization initiator). In this example, silicon oxide particles having an average diameter of 1 μm were used as in Examples 1-9.
    Example 17
    The manufacturing method of a multilayer circuit board using the photosensitive resin composition of this invention as described in Examples 1-17 is demonstrated below with reference to FIG. The multilayer circuit board can be manufactured by the following four steps (1) to (4).
    (1) Formation method of photosensitive film
    The photosensitive film was formed on the surface of the board | substrate 3 with the inner layer circuit 1 using the photosensitive resin composition of this invention so that a circuit might be coat | covered (FIG. 2 (a)). As the substrate 3 having an inner layer circuit, that is, a starting material, a substrate produced by etching a copper plated laminate and forming a circuit by an addition method on the laminate can be used. When copper is used to form the conductor circuit 1, the adhesive force of the conductor circuit 1 with the photosensitive film 2 (and the resin composition material after curing, that is, the insulating film) is determined by the conventional roughening of the copper surface, the formation of the oxide layer, It can increase by reduction of an oxide layer, nickel plating, etc.
    Any one of film forming methods such as dip coating, specific coating, roll coating, knife coating, screen printing and the like can be used. When using the coating method, the solvent is preferably removed by applying the composition to the surface of the substrate and then heating it at a temperature (typically 80 to 120 ° C.) that does not cure the epoxy resin so that the film becomes tacky. . Alternatively, the composition may be previously formed in the shape of a magnetic support film, and the film may be formed by adhering the magnetic support film.
    (2) exposure method and development method
    The film was then exposed through a via-hole mask (not shown in the figure). The unexposed portions were dissolved in the developer and removed to form through-holes for via-hole formation that penetrated through the insulating film 2 and reached the circuits of the lower layer, and then the film was heated at a predetermined temperature (Fig. 2 (b)).
    The photosensitive resin composition of this invention can be developed with the developing aqueous solution excellent in stability and environmental hygiene. The developing aqueous solution suitable for this invention is the aqueous solution of the high boiling point water soluble organic solvent, the aqueous solution of the high boiling point water soluble organic solvent to which the alkaline component was added, etc., for example. As the water-soluble organic solvent, 2-butoxyethanol, 2,2-butoxyethoxyethanol, and the like are suitable. As the alkaline component, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, borax and the like can be used. The concentration of the water-soluble organic solvent is preferably in the range of about 10 to 80% by weight, which is in the non-combustible range, and the concentration of the alkaline component is preferably in the range of 1 to 20% by weight.
    (3) surface treatment method
    Then, the surface of the insulating film 2 (including the inner surface of the through hole 4) was roughened, the roughened residue was removed, the plating catalyst 8 was added, and the surface of the insulating film 2 was activated. (FIG. 2 (c)). The roughening method can be performed with a chromic acid mixture, an aqueous solution of permanganic acid, or the like.
    (4) circuit formation method
    Subsequently, the surface of the insulating film 2 to which the plating catalyst 5 was added is coated with the plating resist 6, exposed through a mask having a predetermined pattern (not shown in the figure), developed, and the resist 6 Is cured by heating under predetermined conditions, the fine conductor circuit is formed by chemical plating using chemical plating and electroplating at the same time, and the plated resist 6 is peeled off. Was formed on the surface of the insulating film 2 (including the inner surface of the through hole 4) (Fig. 2 (d)). In the case where the curing by heating after development is insufficient, after the conductor circuit 7 is formed to enhance the curing of the insulating film 2, it can be post-cured by heating at 160 ° C or higher.
    When forming the conductor circuit layer 7 (planar circuit and via-hole circuit), there are two methods, a total addition method using only chemical plating and a quasi-addition method using both chemical plating and electroplating at the same time. In the present invention, either method may be used. With regard to making circuit rectifiers, the former method is more efficient compared to the latter. However, because the plating liquid is very alkaline and one of the plating conditions is present at high temperatures, many of the conventional photosensitive epoxy resins cannot be used in the electronic method. The photosensitive resin of this invention is excellent in plating solution resistance, and resin can be used efficiently when forming a circuit by the whole addition method.
    According to the method described above, the insulating layer, the circuit for interlayer connection and the planar circuit of the first layer were formed. The multilayer circuit board 9 of the present invention can be obtained by appropriately repeating the methods (1) to (4) to increase the number of layers (Fig. 2 (e)). In the case of using the photosensitive resin composition of the present invention when forming the photosensitive film 2 in the method (1), the photosensitive film 2 adjacent to the through hole 4 from the internal circuit 1 even after roughening and adding a plating catalyst ( And peeling or floating of the insulating film after curing), and forming an inverse tapered phase can also be avoided. The photosensitive resin composition of this invention was excellent at the time of hardening in a layer, and the heat resistance of resin was fully improved. Moreover, the photosensitive resin composition of this invention was excellent in developability, plating solution resistance, etc. Therefore, the photosensitive resin composition of this invention is useful when forming an insertion substrate and a multichip module substrate.
    The multilayer circuit board using the photosensitive resin composition of this invention had high adhesive force between the conductor circuit and the insulating film 2 at high temperature. According to the present invention, since the insulating film 2 fixes the conductor circuit in the multilayer circuit board, it is possible to prevent separation of the conductor circuit due to thermal stress occurring during the solder reflow process and the recovery process. Therefore, a highly reliable high density multilayer circuit can be obtained by the present invention.
    In particular, it is preferable to use the photosensitive resin composition containing a rubber component, an inorganic filler, or a thermosetting agent. For this reason, the high adhesion of the film with the internal circuit can be obtained by reducing the elastic modulus of the film by the effect of the rubber component, and the high adhesion of the film with the conductor circuit formed by plating can be obtained by improving the surface roughening efficiency by the effect of the inorganic filler. have.
    The photosensitive resin composition of this invention is especially suitable for a multilayer printed circuit board because an insulating film with high hardness can be obtained. However, the use of the photosensitive resin composition of the present invention is not limited to the multilayer printed circuit board, but can be applied to the interlayer insulating film, soldering resist or surface passivation film or α-ray protective film of a semiconductor device of a thin film multilayer circuit board. .
    Example 18
    An example of a multilayer printed circuit board is shown in the schematic cross section of FIG. 4, using the photosensitive resin composition of Examples 1 to 17, and having two circuit layers 11 having four layers of inner circuit 1. It formed by the accumulation method in each of both surfaces.
    This example is an example of a multilayer circuit board, in which the multilayer is formed in the same manner as in Example 17 using a core substrate 3 having a four-layer inner layer circuit made by a predetermined method as a starting material. In the core substrate 3 of this embodiment, the thermosetting resin is impregnated into a glass cloth to form a pre-preg, the glaze is applied to the pre-preg, and the three layers of the pre-preg are bonded to the core. It was an insulating layer manufactured by the step of forming the substrate 3. The content of the glass cloth of the insulating layer is preferably 20 to 40% by volume, the relative dielectric constant is preferably in the range of 3.0 to 4.0, and the coefficient of thermal expansion is preferably in the range of 5.0 to 8.0 x 10 -5 / ° C. The core substrate 3 preferably consists of 2 to 4 layers. After the conductor was formed by chemical copper plating on the inner peripheral surface of the through hole wall 10, the through hole 10 was filled with a conductor made of an insulating resin or a mixture of insulating resin and metal powder. The thickness of one layer of the core substrate 3 was in the range of 300 to 400 µm, and the thickness of the internal circuit 1 was in the range of 10 to 30 µm.
    In Examples 1 to 17 above, the thickness of the photosensitive layer 2 was 50 μm. However, the thickness of the photosensitive layer is preferably in the range from 25 to 100 μm, more preferably from 25 to 50 μm. The diameter of the via-holes 4 is preferably in the same range as the thickness of the photosensitive layer 2, ie preferably in the range from 25 to 100 μm, more preferably in the range from 25 to 50 μm.
    Example 19
    Fig. 5 is a schematic cross section showing an example of mounting an LSI by flip mounting on a multilayer printed circuit board obtained in Example 18 using solder balls. In this example, the size was a 10 cm rectangle in planar shape.
    The multilayer circuit board using the photosensitive resin composition of the present invention can be applied to various applications such as substrates for electronic devices such as personal computers, MCM (multi-chip-module) plates, insert plates and the like.
    Furthermore, in addition to the flip chip mounting method shown in this embodiment, CSP (Chip Size Package), BGA (Ball Grid Array) and QFP (Quad Flat Pack package) Various implementation methods of LSI can be used.
    The multilayer printed circuit board of this embodiment can be used as a memory module plate and a disk plate.
    The present invention has provided an insulating film excellent in roughness and adhesion and a photosensitive resin composition and a multilayer printed circuit board capable of forming a via-hole in which the connection is very reliable.
    权利要求:
    Claims (25)
    [1" claim-type="Currently amended] The photosensitive resin composition containing the 1st resin of an epoxy resin, and the 2nd resin which has N-substituted carbamic acid ester atom group in a side chain, and a radical polymerization unsaturated bond.
    [2" claim-type="Currently amended] The photosensitive resin composition of claim 1, wherein the weight ratio of the first resin to the second resin is in the range of 0.8: 1 to 5: 1.
    [3" claim-type="Currently amended] The photosensitive resin composition of Claim 1 whose said 2nd resin is an epoxy resin which has a vinyl ester atom group in a side chain further.
    [4" claim-type="Currently amended] The photosensitive resin composition according to claim 3, wherein the second resin is an epoxy acrylate resin or an epoxy methacrylate resin, wherein at least a portion of the hydroxyl group is substituted with an N-substituted carbamic acid ester atom group.
    [5" claim-type="Currently amended] The photosensitive resin composition of claim 3, wherein the second resin is an oligomer represented by the following Chemical Formula 1 or a halide of the oligomer.
    Formula 1

    Wherein X is hydrogen or a methyl group, Y is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is 0 or 1, and some of R 1 contained in the molecule are N-substituted carbamic acid esters represented by the following general formula (2): Atomic group, the remaining R 1 is a hydroxyl group,
    Formula 2

    In the above formula, R 2 is an alkylene group having 1 to 4 carbon atoms, and Z is hydrogen or an alkyl group having 1 to 4 carbon atoms.
    [6" claim-type="Currently amended] The photosensitive resin composition of claim 3, wherein the second resin is an oligomer represented by the following Chemical Formula 3 or a halide of the oligomer.
    Formula 3

    Wherein X is hydrogen or a methyl group, Y is hydrogen or an alkyl group having 1 to 4 carbon atoms, and some of R 1 contained in the molecule is an N-substituted carbamic acid ester atom group represented by the following Chemical Formula 2, and the remaining R 1 is Is a hydroxyl group,
    Formula 2

    In the above formula, R 2 is an alkylene group having 1 to 4 carbon atoms, and Z is hydrogen or an alkyl group having 1 to 4 carbon atoms.
    [7" claim-type="Currently amended] The photosensitive resin according to claim 5 or 6, wherein the number of N-substituted carbamic acid ester atoms represented by the formula (2) is set in the range of 0.5 to 20, with the number of R 1 in the molecule of the second resin being 100. Composition.
    [8" claim-type="Currently amended] The photosensitive resin composition of Claim 1 in which the said photosensitive resin composition contains a radical photopolymerization initiator further.
    [9" claim-type="Currently amended] The photosensitive resin composition of Claim 8 whose said radical photopolymerization initiator is self cleavable.
    [10" claim-type="Currently amended] The photosensitive resin composition of Claim 8 whose content of the said radical photopolymerization initiator is 0.1-5 weight part with the total weight of the said 1st resin and the said 2nd resin being 100 parts.
    [11" claim-type="Currently amended] The photosensitive resin composition of Claim 1 whose said 1st resin is a polyfunctional epoxy resin.
    [12" claim-type="Currently amended] The photosensitive resin composition according to claim 1, wherein the first resin has an epoxy equivalent in the range of 100 to 500 g / equivalent.
    [13" claim-type="Currently amended] The photosensitive resin composition of Claim 1 which further contains a photo acid generator.
    [14" claim-type="Currently amended] The photosensitive resin composition of Claim 13 whose said photo acid generator is an onium salt.
    [15" claim-type="Currently amended] The photosensitive resin composition according to claim 13, wherein the content of the photoacid generator is in the range of 1 to 10 parts by weight based on 100 parts by weight of the first resin and the second resin.
    [16" claim-type="Currently amended] The photosensitive resin composition of Claim 1 which further contains 3rd resin which has a phenol hydroxyl group.
    [17" claim-type="Currently amended] The photosensitive resin composition of Claim 16 whose said 3rd resin is self-condensation type.
    [18" claim-type="Currently amended] 17. The photosensitive resin composition of claim 16, wherein said third resin is at least any novolak resin, resol resin, hydroxystyrene polymer and hydroxyphenylmaleimide polymer, or any copolymer of said compound.
    [19" claim-type="Currently amended] 17. The photosensitive resin composition according to claim 16, wherein the content of the third resin is in the range of 5 to 30 parts by weight based on 100 parts by weight of the first resin and the second resin.
    [20" claim-type="Currently amended] The photosensitive resin composition of Claim 1 in which a rubber component is contained in the said photosensitive resin composition.
    [21" claim-type="Currently amended] The photosensitive resin composition of Claim 20 whose content of the said rubber component is the range of 5-40 weight part with 100 parts by weight of the total weight of the said 1st resin and said 2nd resin.
    [22" claim-type="Currently amended] The photosensitive resin composition of Claim 1 which is a material for forming the insulating film of a multilayer circuit board.
    [23" claim-type="Currently amended] The insulating film obtained by hardening | curing the photosensitive resin composition of Claim 1.
    [24" claim-type="Currently amended] A multilayer circuit board comprising the insulating film of claim 23.
    [25" claim-type="Currently amended] A multilayer circuit board comprising an inner layer insulating film having a thickness of 30 m or more, a circuit formed on a surface of the inner layer insulating film, and a via-hole having a diameter of 25 m or more through the inner layer insulating film.
    类似技术:
    公开号 | 公开日 | 专利标题
    TWI224488B|2004-11-21|Process for creating vias for circuit assemblies
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    同族专利:
    公开号 | 公开日
    US6190834B1|2001-02-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-05-15|Priority to JP97-125674
    1997-05-15|Priority to JP12567497
    1997-06-05|Priority to JP97-148051
    1997-06-05|Priority to JP14805197
    1998-05-14|Application filed by 우찌가사끼 이사오, 히다찌 가세이 고교 가부시끼가이샤
    1998-12-05|Publication of KR19980087039A
    优先权:
    申请号 | 申请日 | 专利标题
    JP97-125674|1997-05-15|
    JP12567497|1997-05-15|
    JP97-148051|1997-06-05|
    JP14805197|1997-06-05|
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