TW201127238A - Printed wiring board and method of manufacturing the same - Google Patents

Abstract

To provide a high-density printed wiring board including a precise and extremely fine copper circuit pattern formed on a substrate surface, and to provide a method of manufacturing the printed wiring board. The method of manufacturing a printed wiring board includes: (a) a process for performing selective exposure and development to a photosensitive resist film formed on the substrate surface to form a resist pattern (5) that has a formed groove pattern of a portion for circuit formation and can be subjected to nonelectrolytic copper plating; (b) a process for performing nonelectrolytic copper plating to an exposure surface of a substrate of the groove pattern portion and to the entire surface of a patterned resist film and then performing electrolytic copper plating until the surface becomes nearly smooth to form a copper plating layer (7) covering the resist pattern; and (c) a process for uniformly reducing the copper plating layer by mechanical polishing and/or chemical polishing, or etching until the surface of the resist film is exposed to expose a copper circuit pattern (8) on the surface. Preferably, ultraviolet irradiation, heating treatment, and/or plasma treatment are performed to the resist film after pattern formation.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed wiring board and a method of manufacturing the same, and more particularly to a high-density printed wiring board having a fine circuit pattern and a method of manufacturing the same. A printed wiring board for the purpose of mounting an electronic component such as a semiconductor member used in an electronic device, and the ultra-high density of the semiconductor circuit, the wiring width between the circuit conductor and the circuit is required to be further thinned (fine patterning) ). Conventionally, a circuit pattern forming method of a printed wiring board is a copper-clad laminate in which a copper foil or a copper alloy foil (collectively referred to as copper foil in this specification) and an insulating resin are used to form a copper-clad laminate on the surface of the copper foil. After the photosensitive resist film, selective exposure and development are performed to remove the resist film, and secondly, the exposed portion of the copper box is removed by squeezing, and the so-called etch method is formed to be thinner than 5 // m. After forming a photosensitive resist film on the surface of the resin for insulating the copper film, the resist film is removed by selective exposure and development to remove the circuit formation portion. Next, the exposed thin copper film is used as a plating electrode, and copper is plated by electric copper plating. The ruthenium is buried in the resist removal portion, and after the resist film is removed, the entire surface is uniformly etched to completely remove the thin copper film on the surface of the insulating resin, thereby forming a circuit composed of a portion formed by electroplating. The so-called semi-subtractive method or semi-adjusted method is to form an electroless resist film on the surface of the insulating resin to form a photosensitive resist film -5, 201127238' Selective exposure, development removes the resist film forming part of the circuit, and then forms a copper circuit only in the portion of the resist removed by electroless copper ore. The so-called fulladditive method is further used as an electrode for electric ore. The surface of the metal plate is selectively formed with a plating resist film, and secondly, a copper plating layer is formed by plating on a portion where the resist film is not formed, to remove the resist film or the resist film is not removed, and the semi-curable resin is simultaneously performed. The method of forming a circuit in the form of a resin-embedded copper circuit by removing a metal plate is known (for example, refer to Patent Document i 4). However, any of the aforementioned conventional In the method, since the copper circuit pattern is formed by selective etching or selective plating in a restricted area, the width precision, economy, mass productivity, and the like of the circuit are limited, so that it is required to be manufactured in a more economical and rational manner. High density copper circuit pattern technology. [Patent Document 1] JP-A-2003-249751 [Patent Document 2] JP-A-2003-298243 [Patent Document 3] JP-A-2004-193458 (Patent Document 4) JP-A-2007- 242 975 SUMMARY OF THE INVENTION In view of the conventional techniques as described above, an object of the present invention is to provide a method for producing a printed wiring board which can be used for various thermosetting resin composition laminates or thermosetting resin composition films. The surface of the substrate is -6-201127238, and a copper circuit pattern of extremely fine lines with high precision and economy is produced. Further, an object of the present invention is to provide a high-density printed wiring board having a high-precision and extremely fine copper circuit pattern manufactured by such a method. In order to achieve the aforementioned object, the manufacture of a printed wiring board according to the present invention is provided. The method comprises the following steps: (a) selectively exposing and developing a surface of a substrate on which a photosensitive resist film is formed to form a groove pattern in which a circuit forming portion has been formed, and forming a copper plating layer by electroless copper plating (b) electroless copper plating is performed on the exposed surface of the substrate of the groove pattern portion and the entire surface of the patterned resist film, and then the electrolytic copper shovel is performed until the surface is substantially smooth. a process for forming a copper plating layer covering the resist film; and (c) until the surface of the resist film is exposed, and the copper plating layer is uniformly reduced by mechanical honing and/or chemical honing or etching. A process in which a copper circuit pattern is exposed from a surface. In other embodiments, after the above process (C), (d) a process of removing the resist film such that the surface layer portion is only a copper circuit pattern. In the process (d), the resist film is peeled off with an alkaline aqueous solution or removed by a stripping treatment. In a good embodiment, the substrate should have a surface on which the copper foil of the copper-clad laminate is etched to transcribe the surface of the copper foil. In another preferred embodiment, after the resist film is patterned, at least one of the treatments selected from the group consisting of ultraviolet irradiation, heat treatment, and plasma treatment 201127238 may be performed, and electroless copper plating may be used. A resist film of a copper plating layer is formed. In the above-described process (a) of the other preferred embodiment, the photosensitive resist film formed on the surface of the substrate is subjected to selective exposure by direct exposure of ultraviolet pattern or ultraviolet light, and secondly, development is performed to form a circuit forming portion. Ditch pattern. In addition, the substrate used in the above process (a) needs to be blended and has a through hole. When a multilayer printed wiring board is further produced, after the process (c), a photosensitive resist film is further formed after the interlayer resin insulating layer is formed, and the processes (a), (b) and (c) are repeated. Alternatively, after the above process (d), a photosensitive resist film is further formed after the formation of the interlayer resin insulating layer, and then the processes (a), (b) and (c) are repeated to form a multilayer printed wiring board. At this time, the above-described processes (a), (b), and (c) are repeated, and the resist film removing process of the above (d) may be further carried out so that the surface layer portion is only a copper circuit pattern. Further, according to the present invention, there is provided a printed wiring board characterized by having a resin insulating layer which is formed by any of the above methods and which is buried between a copper circuit pattern of a surface layer portion and the pattern, and the copper circuit The pattern and the resin insulating layer form a flat surface. The method for manufacturing a printed wiring board of the present invention is different from the conventional method of forming a copper circuit by selective etching or selective plating using a restricted region, and selectively exposing the photosensitive resist film formed on the surface of the substrate. The pattern of the groove forming the circuit forming portion can be formed by electroless copper plating to form a patterned resist film of the copper plating layer, and the substrate of the groove pattern portion is exposed -8 - 201127238 surface and the entire surface of the patterned resist film is covered The electroless copper plating layer is subjected to electrolytic copper plating until the surface is substantially smooth, and after the copper plating layer covering the resist film is formed, the surface of the resist film is exposed, and mechanical honing and/or chemistry is performed. The honing or etching uniformly reduces the overall copper plating layer to expose the copper circuit pattern from the surface, so that the entire process requires no special processes or materials, but good precision can be used to form a high-precision fine circuit pattern. According to this method, an extremely fine copper circuit up to a width of 5 μm can be easily formed, and the resist film forming process for forming the groove pattern, the electrolytic copper plating process for electroless copper plating, and the whole can be repeated. When a honing or etching process is used to fabricate a multilayer printed wiring board, since the photosensitive resist is used for the regulation of the circuit pattern region, the alignment accuracy of the upper upper layer copper circuit pattern can be obtained. Further, the obtained printed wiring board has excellent circuit width accuracy and reliability, and is also suitable for use in the manufacture of a substrate for mounting a semiconductor wafer and an ultrahigh-density printed wiring board. [Embodiment] As described above, the method for manufacturing a printed wiring board of the present invention is different from the conventional method of forming a copper circuit by selective etching or selective plating using a limited area, and is sensitive to the surface formed on the substrate. The selective resist film is selectively exposed and developed to form a groove pattern of the circuit forming portion, so that electroless copper plating can be performed, that is, a copper plating layer can be formed by electroless copper plating, and the patterned resist film can be formed. Electroless copper plating is performed on the exposed surface of the substrate on the groove pattern portion and the entire surface of the patterned resist film, and then electrolytic copper plating is performed until the surface is substantially smooth, thereby forming a copper plating covering the resist-9 - 201127238 film. After the layer, until the surface of the resist film is exposed, the entire copper plating layer is uniformly reduced by mechanical honing and/or chemical honing or etching, and the copper circuit pattern is exposed from the surface. In general, the conventional copper circuit pattern formation method is based on the premise that plating (catalyst) does not adhere to the surface of the anti-touch film formed by the commercially available electroplating resist, so that no resist film exists. Part of the plating is formed to design. The inventors of the present invention have made an electric shovel layer on the surface of a resin containing a base material of a resist film, and have carefully reviewed it. As a result, it has been found that electroless copper plating can be performed as long as it is moderately treated. In particular, the irradiation is stronger than the ultraviolet rays at the time of exposure, or the pretreatment such as heating at a temperature equal to or higher than the glass transition temperature (Tg) of the resist film, or plasma treatment such as argon or oxygen. By performing such pretreatment, electroless copper plating can be deposited not only on the resist film, but also dissolution and the like, and contamination of the plating solution can be reduced, and discoloration of the electroless plating surface, poor gloss, and plating of pinholes can be achieved. . Further, it is possible to suppress the alkali resistance and the swelling of the resist film, and the shape of the formed circuit is also relatively stable and confirmed. It can achieve unexpected results that are unexpected. Hereinafter, a method of manufacturing the printed wiring board of the present invention will be specifically described with reference to the attached drawings.

First, as shown in Fig. 1(C), the substrate 1 on which the photosensitive resist film 4 is formed is prepared. Further, in the first (C) drawing, the substrate 1 on which the photosensitive resist film 4 is formed on both surfaces is used. However, the substrate on which the photosensitive resist film 4 is formed on one side may be used. The substrate 1 is not particularly limited as long as it is a substrate known as a printed wiring board. Specifically, for example, non-woven fabrics, woven fabrics, etc. of glass fibers, such as E, NE, D, S, and T glass, which are defined in JIS-10-201127238, are impregnated with, for example, epoxy resin and polyfluorene. One or more of an imide resin, a cyanate resin, a maleimide resin, a double bond-bonded polyphenylene ether resin, a resin composition containing a bromine or a phosphorus compound, or the like, if necessary The substrate is cured by impregnating a thermosetting resin composition such as a catalyst, a hardener, a hardening accelerator, or the like which is well known. Further, a resin substrate such as a polyimide, a bismaleimide-triazole resin substrate, a fluororesin substrate, or a polyimide film, a PET film, a ceramic substrate, or a wafer substrate can be used. Wait. In order to improve the adhesion to the photosensitive resist film by forming a flat surface having fine irregularities on the surface thereof, it is also possible to carry out a well-known roughening treatment, for example, using a base such as an aqueous sodium hydroxide solution. Swelling of a solution, treatment with a solution containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and a series of chemistry such as treatment with an aqueous solution of sulfuric acid or hydrochloric acid Treatment (oxidant treatment). For the roughening treatment, it is also possible to use a commercially available degumming solution (roughening agent). However, in particular, it is preferable to use the copper-clad laminate 3 to which the copper foil 2 is bonded to both surfaces of the substrate 1 as shown in Fig. 1 (A), and to remove all the copper foils 2, and to have the first (B) The substrate 1 on which the surface of the copper foil uneven surface is transcribed is shown. In this case, the surface of the substrate on which all the copper foils 2 are removed by etching is removed without the need for the roughening treatment, and the photosensitive resist film 4 can be formed directly with good adhesion. Therefore, the wiring board can be sufficiently reliable. The copper-clad laminate 3 can use all of the copper-clad laminates conventionally known, however, it is also suitable to use the following composite-shaped copper-clad laminates, that is, in a copper box or a resin composite copper box, for example - A resin composite copper foil containing a resin layer of a block copolymerized polyimine resin and a polymaleimide compound is formed on one surface of a copper foil described in Japanese Laid-Open Patent Publication No. 2007-242975. On the resin layer, a layer B resin composition layer is laminated. The copper foil used in the resin composite copper foil is not particularly limited as long as it is a copper foil known for use in a printed wiring board. However, it is preferable to use an electrolytic copper foil, a rolled copper foil, or the like. Alloys, etc. As the copper foil, a surface treatment person known as, for example, nickel, cobalt treatment, decane treatment agent or the like can be used. The thickness of the copper foil is not particularly limited, and is preferably 3 5 /z m or less. The surface roughness (Rz) of the surface of the copper foil on which the resin layer is formed is preferably 4 μm or less, more preferably 2 #m or less. Here, "Rz" is the ten-point average thickness specified in JIS B0601. In addition, it is also possible to form a well-known layer of the copper foil. The method of etching away all of the copper foil 2 of the copper-clad laminate 3 can be carried out by a well-known method. The etching liquid is not particularly limited. However, an aqueous solution of sulfuric acid-hydrogen peroxide, an aqueous solution of persulfate such as ammonium persulfate, sodium persulfate or potassium persulfate, and an aqueous solution of ferric chloride or copper trichloride are suitably used. As described above, the photosensitive resist film 4 is formed on the surface of the substrate 1 on which the fine uneven surface is formed. The photosensitive resin composition used for forming the photosensitive resist film 4 may be in the form of a dry film in which a dried coating film is formed on the carrier film, or may be in a liquid state diluted in a solvent. When the film is dry, it is attached to the substrate by a hot roll laminator and a vacuum laminator at a temperature of about 40 to 130 ° C. When it is in a liquid state, it is screen-printed, spray-coated, and die-cast. Cloth, slit coater, curtain coater, roller coater -12- 201127238, etc., coating, at a temperature of about 60~150 °C, the hot air circulation type far infrared ray is carried out for about 1 to 30 minutes. The photosensitive resist film 4 which is not adhered can be formed by drying to evaporate the solvent. At this time, the film thickness of the light anti-uranium film 4 should be in the range of about 3 to 30 # m, preferably 2 times or less of the minimum line width of the circuit, preferably, etc. Further, the photosensitive resist film 4, for the subsequent electroless copper plating electrolytic copper plating catalyst fixed with sufficient alkali resistance and adhesion for the film used for the production of dry film, polyethylene terephthalate thermoplastic resin film is preferred, It is possible to use 10 to 50 vm. In order to have good rationality, a film thickness of 25 to 5 Å/m is obtained for good resolution, and a film thickness of 10 to 2 5 /zm is preferred. The difference should be designed such that the refractive index of the photosensitive resist film is 1.  1. 55~1. A dry film of a better range of 60, even if the carrier film is of good resolution. The photosensitive resin group used for forming the photosensitive resist film 4 is used by developing an exposed portion (the portion irradiated with the active energy ray) to remove the negative photosensitive resin composition of the unexposed portion; or having a crosslinked structure and being insoluble. In the developer, the exposed portion may be any one of the positive photosensitive resin compositions which are decomposed by the acid generated by the acid compound which is generated by the energy ray. In view of environmental problems, the lipid composition is preferably an alkali-developable photosensitive resin composition using a liquid as a developing solution, and preferably a resin having a carboxyl group. For example, the positive-type photosensitive resin composition can be used, for example, in a drying oven or (temporarily dry-formed by electroplating.) The process is not good. The thickness range of ethylenediester is good, in order to eliminate 50 or more, thick A film-forming carboxyl group-containing film described in Japanese Unexamined Patent Application Publication No. Hei No. Hei No. Hei. a resin, a homopolymer of an unsaturated monomer containing a carboxyl group polymer, a copolymer of a monomer and other copolymerizable monomer, a polyester system having a carboxyl group at a molecular chain molecule end, and a polyamine a compound containing a carboxyl group-containing resin and a polyamine-containing carboxyl group-containing resin, and a compound containing two or more vinyl ether groups in one molecule, and a compound containing an acid generated by irradiation with an active energy ray (photoacid-based photosensitive resin composition is required as a component) A resin composition containing a resin obtained by reacting a monovinyl ether compound with a polycarboxylate and a photoacid generator as an essential component, as exemplified by Japan, as disclosed in Japanese Laid-Open Patent Publication No. 2 72923 A polyacetal ester (P〇ly hemiacetal ester) obtained by an addition polymerization reaction of a dicarboxylic acid and a divinyl ether compound described in the publication No. 403 1 5, and a photoacid generator are used as a photosensitive resin composition. Such as the international publication w 0 9 9 - 1 5 9 3 5 A containing phenolic hydroxyl group or sulfhydryl soluble polymer, vinyl ether compound, and photoacid generator as the photosensitive resin A negative photosensitive resin composition having an exposed portion which is cured by irradiation with an active wire remains, and the carboxyl group-containing resin used can be subjected to electroless copper plating without performing the previous treatment described later. The negative photosensitive resin composition contains (A) a carboxyl group-containing, (B) photopolymerization initiator, and (C) a photosensitive monomer, and remains without removing the photosensitive resist film between the copper circuits. When the insulating layer is used, it is preferable to add (D) a thermosetting resin and (E) a coating material. The carboxyl group-containing resin (A) can be used to impart an alkalinity, for example, a carboxyl group or the like. 10- Acid tree light contains half shrinkage The base described is a must-have energy, and the resin is a residue-containing resin which is known in the art to have a carboxyl group in the molecule for the purpose of photoinhibition-14-201127238. In particular, from photohardenability and In terms of both developability, it is preferred that the carboxyl group-containing photosensitive resin (Α·1) having an ethylenically unsaturated double bond in its molecule is bonded. Secondly, its unsaturated double bond should be derived from acrylic acid or methacrylic acid or In addition, when only the carboxyl group-containing resin (Α-2) having no ethylenic unsaturated double bond is used, in order to make the composition photohardenable, it is necessary to use two or more of the molecules described later. The ethylenically unsaturated group compound (C), that is, the photosensitive monomer must be used. In addition, the refractive index is 1. 50~1. In the case of 60, a carboxyl group-containing resin (Α) having a structure having an aromatic ring in the molecule is preferred because it has a good resolution in view of the refractive index of the carrier film described above. The carboxyl group-containing resin having an aromatic ring can be used for styrene-containing (meth) acrylates such as styrene and its derivatives, oxime structure, diphenylethylenedione (meth) acrylate, and various (meth) groups. A conjugate of an acrylate copolymer and various acid-modified epoxy (meth) acrylates, an alkylene oxide modification of various phenol resins, an acid anhydride, and a carboxyl group-containing resin (A), such as the compounds listed below ( It can also be either an oligomer or a polymer). (1) A carboxyl group obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid or an unsaturated group-containing compound such as styrene, α-methylstyrene, a low alkyl (meth) acrylate or isobutylene Resin. (2) a diisocyanate such as an aliphatic diisocyanate, a divalent aliphatic diisocyanate, a ring-shaped diisocyanate or an aromatic diisocyanate, and a carboxyl group-containing diethanol compound such as dimethylolpropionic acid or dimethylolbutanoic acid- 15-201127238, and polycarbonate-based polyalcohol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, propylene-based polyol, bisphenol A-based alkylene oxide derivative diol, and phenolic A carboxyl group-containing urethane resin obtained by addition polymerization of a diol compound such as a hydroxyl group and an alcoholic hydroxyl group (3) Aliphatic diisocyanate, divalent aliphatic diisocyanate, ring diisocyanate, aromatic diisocyanate a diisocyanate compound, a polycarbonate-based polyalcohol, a polyether-based polyalcohol, a polyester-based polyalcohol, a polyolefin-based polyalcohol, a propylene-based polyalcohol, a bisphenol A-based alkylene oxide derivative diol, or the like A terminal carboxyl group-containing urethane resin obtained by reacting a terminal of a urethane resin obtained by an addition polymerization reaction of a diol compound such as a phenolic hydroxyl group and an alcoholic hydroxyl group with an acid anhydride. (4) Diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, A carboxyl group-containing photosensitive potassium compound obtained by addition polymerization of a (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing diethanol compound, and a diol compound, such as a bisphenol type epoxy resin Acid ester resin. (5) In the polymerization of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth)acryl fluorenyl groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. It is a terminal (meth) acrylated carboxylated urethane resin. (6) In the polymerization of the resin of the above (2) or (4), one of the molecules such as isophorone diisocyanate and pentaerythritol triacrylate is added. An isocyanate group (-16-201127238 isocyanate group) and one or more (meth)acryloyl group-based compounds, and a terminal (meth) acrylated carboxyl group-containing urethane resin. (7) reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin of a bifunctional or higher functional group described later, and adding a 2-basic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrofurfuric anhydride A carboxyl group-containing photosensitive resin is present in the hydroxyl group present in the side bond. (8) reacting (meth)acrylic acid with a polyfunctional epoxy resin which further epoxidizes a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin described later, and attaches 2 to the generated hydroxyl group. A salt-based acid anhydride is a carboxyl group-containing photosensitive resin. (9) adding a cyclic ether such as a cyclic ether of ethylene oxide to a polyfunctional phenol compound such as phenolic acid, such as a cyclic carbonate of propylene carbonate, and partially esterifying the obtained hydroxyl group with (meth)acrylic acid to make a multi-salt The base acid anhydride reacts with the residual hydroxyl group to form a carboxyl group-containing photosensitive resin. (1) The resin of the above (1) to (9) is further added to a molecule such as glycidyl (meth) acrylate or α-methyl glycidyl (meth) acrylate. A compound containing one or more (meth) acrylonitrile groups and a carboxyl group-containing photosensitive resin. The use of the carboxyl group-containing resin (A) is not limited to the above-described examples, and may be used alone or in combination of several kinds. Further, in the present specification, the term "(meth)acrylate" is used collectively to refer to the terms of acrylate, methacrylate and a mixture thereof, and the like is the same. Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the main chain·polymer-17-201127238, it can be developed with an aqueous alkaline solution. Further, the acid-containing oxime of the carboxyl group-containing resin (A) should preferably be in the range of 30 to 150 mgKOH/g, more preferably 40 to 110 mgKOH/g. When the acid hydrazide of the carboxyl group-containing resin is less than 30 mgKOH/g, the solubility in the alkaline aqueous solution is lowered, and the formed coating film is difficult to develop. On the other hand, if it is higher than 150 mg K: OH/g, the developer is excessively dissolved in the exposed portion, and the line is too thin, or the exposed portion and the unexposed portion are indistinguishable from being dissolved by the developer, and sometimes it is difficult to form a normal one. Resist pattern. Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin substrate, and is generally preferably 2,000 to 150,000, more preferably 5,000 to 100,000. The weight average molecular weight is 2,000 or less, the non-adhesive property may be inferior, the moisture resistance of the coating film after exposure is not good, and film reduction may occur at the time of development, and the resolution is greatly lowered. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is deteriorated. The blending amount of the carboxyl group-containing resin (A) should be 20 to 80% by mass, preferably 30 to 60% by mass based on the total composition. When the blending amount of the carboxyl group-containing resin (B) is less than the above range, the film strength is lowered. On the other hand, when the amount is more than the above range, the viscosity of the composition is high, which may result in a decrease in coatability or the like. . The photopolymerization initiator (B) can be used by a person skilled in the art. Further, it is also possible to use a conventionally known photoinitiator and a sensitization IJ. Examples of specific photopolymerization initiators, photoinitiating aids, and sensitizers 'Example-18- 201127238 For example, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, diphenyl A ketone compound, a xanthone compound, a tertiary amine compound, and the like. Specific examples of benzoin compounds, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. Specific examples of the acetophenone compound, for example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2·diethoxy-2-phenylethyl benzene, 1, 1-Dichloroacetone. Specific examples of the hydrazine compound are, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-t-butylhydrazine, 1-chloroindole. Specific examples of thioxanthone compounds, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone Specific examples of the ketal compound are, for example, acetophenone dimethyl ketal, diphenylethylenedione dimethyl ketal. Specific examples of the diphenyl ketone compound, for example, diphenyl ketone, 4-benzylidene diphenyl sulphide, 4-benzylidene-4'-methyldiphenyl sulphide, 4-phenylidene fluorenyl _ 4 '-Ethyl diphenyl sulfide, 4-benzylidene-4'-propyl diphenyl sulfide. Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaniline structure, for example, 4,4'-dimethylamine diphenyl ketone (NISSO CURE-MABP, manufactured by Nippon Soda Co., Ltd.), 4 , 4, diethylamine diphenyl ketone (HODOGAYA CHEMICAL CO. ,LTD. Dialkylamine diphenyl ketone, 7-(diethylamine)-4-methyl-2H-1-benzopipene-2-one (7-(diethylamine)-4) _Methyl bean fragrant), etc. -19- 201127238 Soybean compound containing dialkylamine group, ethyl 4-dimethylamine benzoate acid (NIPPON KAYAKU CO. , LTD. KAYACURE - EPA ), 2-dimethylamine benzoic acid ethyl (INTERCATIONAL BIO-SYNTHETICS Quantacure DΜB), 4-dimethylamine benzoic acid (n-butoxy) ethyl (INTERNATIONAL BIO-SYNTHETICS Quantacure BEA), p-dimethylamine benzoic acid isoamyl ethyl vinegar (NIPPON KAYAKU CO. ,LTD. KAYACURE-DMBI), 4-dimethylamine benzoic acid 2-ethylhexyl (Esolol 507 manufactured by Van Dyk Co., Ltd.), 4,4'-diethylamine diphenyl ketone (EADOGAYA CHEMICAL CO·, LTD. ). In addition to the photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, an acyl phosphine oxide photopolymerization initiator, an oxime ester photopolymerization initiator, or the like can be used. α-Aminoacetophenone photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinone-1,2-diphenylethylenedione -2-dimethylamine-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamine)-2-[(4-methylphenyl)methyl]· 1-[4-(4-morpholino)phenyl]-1-butanone, hydrazine, hydrazine-dimethylamine acetophenone, and the like. City merchandise, IRGACURE-907, IR G A C U R E - 3 6 9, IRGACURE-379, etc., manufactured by CIBA JAPAN. Acyl phosphine oxide photopolymerization initiator 'for example 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl oxidation Phosphine, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, etc., commercially available, for example, Lucirin TPO, CIBA JAP AN, manufactured by BASF The system of IR GACUR E-819 and so on. An oxime ester photopolymerization initiator 'for example, 2-(ethenyliso-20- 201127238 nitrosomethyl) thioxan-9-one, etc., commercially available product 'for example, CGI-325 manufactured by C IB AJAPAN Co., Ltd. , IRGACURE-OXEOl, IRGACURE-OXE02, N-1919 made by ADEKA. Representative photopolymerization initiators are listed above. However, those which can generate a base active center or contribute to the growth of the species by light irradiation are not limited to those described above. Further, although the base itself does not generate a base, it is also possible to use a conventionally known sensitizer which has a sensitizing effect on the above photopolymerization initiator. The photopolymerization initiator, the photoinitiator, and the sensitizer may be used singly or in combination of two or more. In addition, the blending amount of the photopolymerization initiator, the photoinitiating aid, and the sensitizer is sufficient in a usual amount, and generally, it is 100% by mass based on the carboxyl group-containing resin (A) (two or more types are used). The carboxyl group-containing resin is the total amount, the same as the following), and should be 0. 01 to 30% by mass, preferably at 0. A range of 5 to 15% by mass. When the photopolymerization initiator (B) is blended in an amount of 〇·〇 of 1% by mass or less, the photocurability is insufficient, and the coating film is peeled off, or the coating properties such as chemical resistance are lowered. On the other hand, when the amount is more than 30% by mass, the light absorption on the surface of the coating film of the photopolymerization initiator (B) is sharply increased, and the deep curing property tends to be lowered. The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photosensitive resin composition of the present invention is photohardened by irradiation with an active energy ray, and the carboxyl group-containing resin (A) is insoluble or assisted. It is insoluble in an aqueous alkaline solution. Such a compound, for example, a diacrylate of ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, three Hydroxy-21 - 201127238 Polyols such as ethyl isocyanurate or polyvalent acrylates such as these ethylene oxide addition products or propylene oxide addition products; phenoxy acrylate, bisphenol A a polyvalent acrylate such as a diacrylate or an ethylene oxide addition product or a propylene oxide addition product of the phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane tricondensate A polyvalent acrylate of a glycidyl ether such as a glyceryl ether or a triglycidyl isocyanurate; and a melamine acrylate and/or each methacrylate corresponding to the above acrylate may be used alone or in combination of two or more. . Further, for example, an epoxy acrylate resin in which acrylic acid is reacted with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and a hydroxy acrylate such as pentaerythritol triacrylate or isophorone diisocyanate. An epoxy urethane acrylate compound in which a half-isocyanate compound of a diisocyanate reacts with a hydroxyl group of the epoxy acrylate resin. Such an epoxy acrylate-based resin can improve the light-hardenability without lowering the dust-free property. The blending amount of the compound (C) having two or more ethylenically unsaturated groups in the molecule should be 5 to 100% by mass, preferably 1 to 7 based on 100% by mass of the carboxyl group-containing resin (A).比例% by mass. When the blending amount is 5% by mass or less, the photocurability is lowered, and it is difficult to form a pattern by alkaline development after the active energy ray irradiation. On the other hand, when the content is more than 100% by mass, the solubility in the alkaline aqueous solution is lowered, and the coating film becomes brittle. In addition, the photosensitive resin composition used in the present invention may be provided with thermosetting property in order to impart heat resistance. Ingredient (D). For the thermosetting component (D), an amine resin such as a melamine resin or a benzoquinone resin, a double horse-22-201127238, a sulfonium compound, an oxoazobenzoic compound, an oxazoline compound, a carbonized secondary product can be used. A commonly known thermosetting resin such as an amine resin, a blocked isocyanate compound, a cyclocarbonate compound, a polyfunctional epoxy compound, a polyfunctional oxycyclobutane compound, an episulphide resin, a melamine derivative, and the like . Among these, the most preferable thermosetting component (D) has two or more cyclic ether groups and/or cyclic ethyl sulfide groups (hereinafter, simply referred to as a cyclic (ether) ether group) in one molecule. The thermosetting component is, for example, a polyfunctional epoxy compound having two or more epoxy groups in the molecule, a polyfunctional oxycyclobutane compound having two or more epoxy butyl groups in the molecule, and two or more molecules in the molecule. Ethyl sulfide based episulphide resin. The blending amount of the thermosetting component (D) should be 〇·6~2 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). 5 equivalents, preferably at 0. 8~2. 0 equivalent range. When the photosensitive resin composition contains the thermosetting component (D) as described above. It should further contain a heat hardening catalyst. Such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, cardiophenylimidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenylimidazole and 1-(2-cyanoethyl)-2·ethyl-4-methylimidazole; dicyandiamide, diphenylethylenedione dimethylamine, 4- (dimethylamine)-oxime, Ν-dimethyldiphenylbenzylamine, 4-methoxy-oxime, Ν-dimethyldiphenylbenzylamine, 4-methyl-oxime, Ν- An amine compound such as dimethyldiphenylbenzylamine, an anthracene acid adipate or a phosphonium azelate or the like; a phosphorus compound such as triphenylphosphine or the like. In addition, the city's goods, for example, manufactured by Shikoku Chemical Industry Co., Ltd., 2ΜΖ-Α, 2ΜΖ-0Κ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2P4MHZC are all known as imidazole compounds, -23-201127238), U-made by SAN-APRO LIMITED CAT (registered trademarks 3 5 03N, U-CAT3502T (all trade names of dextro-isocyanate dimethylamine), DBU, DBN, U-CATSA102 CAT5 002 (all are bicyclic hydrazine compounds and In particular, it is limited to the above, and may be used alone as long as it is a thermal catalyst of an epoxy resin and an oxycyclobutane compound, or may promote an epoxy group and/or an epoxybutyl group and a carboxyl group. It is also possible to use a mixture of two or more kinds. In addition, guanamine, acetoguanamine, benzoquinone, cyanamide, 2,4-diamine-6-methacryloyloxyethyl ester are also used. -S-triazastyryl-2,4-diamine-S-triazabenzene, 2-vinyl-4,6-diamine-S-heterobenzene-isocyanuric acid addition product, An S-triaza complex such as a 2,4-diamine-6-methacryloylethyl ester-S-triazabenzene-iso-cyanuric acid addition product, preferably having such a close adhesion property Compound function and thermosetting For the use of the catalyst, the amount of the thermosetting catalyst is usually sufficient, for example, the thermosetting property of the carboxyl group-containing resin (A) or more than # cyclic (sulfur) ether groups in the molecule. Ingredient (D)% by mass, should be 〇.  1 to 2 0% by mass, preferably 0. 5~1 5. 0% by mass» The photosensitive resin composition used in the present invention is blended with the material (E) in order to improve the physical strength and the like. In this case, conventionally known inorganic or organic tanning materials can be used, however, barium sulfate, spheroidal vermiculite and talc are preferred. Further, in order to obtain an appearance and flame retardancy, titanium oxide, a metal oxide or a metal hydroxide hydroxide can also be used as a body pigment pigment. The blending amount of the dip material is 75 mass% or less, preferably 0. 1~60 mass standard) Salinization, U- is not hardened, then the ratio of trimeric and 2-triazobenzene can be increased by I: there are 2 1 00 coating film and white aluminum, etc., should: %-24 - 201127238 ratio. When the blending amount of the coating material exceeds 75 mass% of the total amount of the composition, the viscosity of the insulating composition is high, and the coating and moldability are lowered, and the cured product is brittle, which is not preferable. The photosensitive resin composition used in the present invention may contain a ketone, an aromatic hydrocarbon, a glycol ether, a glycol ether acetate, or the like, in order to prepare a composition or to adjust the viscosity of the substrate and the carrier film. Various organic solvents such as esters, ethanols, aliphatic hydrocarbons, and petroleum solvents. In addition, if necessary, it is possible to mix conventional polymerization inhibitors such as hydroquinone, benzenediol monomethyl ether, t-butyl catechol, benzenetriol, thiodiphenylamine, and fine powdered vermiculite. Organic bentonite, montmorillonite, etc. commonly known as tackifiers, pigments, dyes, lanthanides, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole, thiazole, triazole It is a conventionally known additive such as a decane coupling agent, an oxidation inhibitor, and a rust inhibitor. (1) The patterned resist film forming process is as shown in the above-mentioned first (C) diagram, and the substrate 1 on which the photosensitive resist film 4 is formed on the surface is formed, and the through hole 6 is formed by opening the hole. Selective exposure and development, as shown in Fig. 2(A), a patterned resist film for forming a copper plating layer by electroless copper plating to form a groove pattern forming a circuit forming portion (hereinafter, simply referred to as resist Film or resist pattern) 5. When the photosensitive resist film 4 is formed using the negative photosensitive resin composition, the unexposed portion is removed by development, and when the positive photosensitive resin composition is used, the exposed portion is removed by development. Selective exposure, contact (or non-contact), selective exposure to the active energy line through the patterned mask, or -25-201127238, can also be directly exposed by laser direct exposure machine . In addition, when the photosensitive resin composition used for forming the photosensitive resist film contains the thermosetting component (D), it can be further heat-hardened to improve the heat resistance, chemical resistance, and moisture absorption resistance of the resist film. Characteristics such as adhesion and electrical characteristics. The exposure machine used for the above active energy ray irradiation can use a direct drawing device (for example, a laser direct imaging device that uses a CAD data from a computer to directly image a laser), an exposure machine equipped with a metal halide lamp, and a matching machine. An exposure machine for carrying (ultra) high-pressure mercury lamps, an exposure machine equipped with a mercury arc lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp. The active energy ray can be either a gas laser or a solid laser as long as it uses laser light having a maximum wavelength of 3 5 0 to 41 Onm. Further, the exposure amount varies depending on the film thickness or the like, but is usually in the range of 5 to 200 mJ/cm 2 , more preferably 5 to 100 mJ/cm 2 , and most preferably 5 to 50 mJ/cm 2 . For the direct drawing device, for example, a product manufactured by ORB OTECH Co., Ltd., PENTAX Corporation, or the like can be used, and any device can be used as long as it oscillates laser light having a maximum wavelength of 3 50 to 410 nm. As the developing method, a dipping method, a shower method, a spraying method, a brush method, or the like can be employed. The development may be a solvent development, but it is preferably carried out by using an aqueous alkaline solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, aqueous ammonia or an amine. (2) The electroless copper plating electrolytic copper plating process is performed on the exposed surface of the substrate 1 of the groove pattern portion and the surface of the resist pattern 5 -26-201127238 as a whole, by a well-known method such as the second (B) As shown in the figure, electroless copper plating is performed, and secondly, until the surface is substantially smooth, electrolytic copper plating is performed to form a copper plating layer 7 covering the resist pattern 5. At this time, before the electroless copper plating, the treatment is performed for the purpose of forming electroless copper plating on the surface of the resist pattern 5, and the resist pattern 5 after development should be irradiated with ultraviolet rays stronger than that at the time of exposure, or It is heated to a temperature higher than the glass transition temperature (Tg) of the anti-contact film, or subjected to plasma treatment such as argon or oxygen. By performing the above pretreatment, not only electroless copper plating can be deposited on the resist pattern 5, but also elution can be reduced, and the contamination of the electroplating liquid can be suppressed, and the discoloration of the electroless plating surface, poor gloss, and pinhole plating can be achieved. Precipitate. Further, it is also possible to suppress alkali resistance and swelling of the resist film, and the shape of the formed circuit is also relatively stable. Electroless copper plating 'Generally, a planing medium is supplied to the exposed surface of the substrate and the entire surface of the patterned resist film, and then immersed in an electroless copper plating solution to form a copper layer. The thickness of the electroless copper plating layer is generally about 〇. 5 ~ 2 / m range. In addition, after forming an electroless copper plating layer, it is heat-treated at 100 ° C to 200 ° C. The heating time is not particularly limited and can be selected between 30 minutes and 5 hours. In order not to oxidize the copper foil, it is preferred to carry out heating in a vacuum or in an inert gas. Next, immersed in an electrolytic copper plating solution, as shown in Fig. 2(B), an electrolytic copper plating layer covering the resist pattern 5 and having a substantially smooth surface of the copper plating layer 7 is formed. The thickness of the electrolytic copper plating layer can be arbitrarily selected. (3) Etching Process -27- 201127238 As shown in the second (B) diagram, after the copper plating layer 7 is formed, as shown in the second (C), the surface of the resist pattern 5 is exposed, mechanically honed and / or chemical honing or etching to uniformly reduce the copper plating layer 7 to expose the copper circuit pattern 8 from the surface. Thereby, the upper and lower copper circuit patterns 8 are in a state of being connected via the plating through holes 9. Mechanical honing and/or chemical honing can be carried out by a conventionally known method. Further, the etching solution is not particularly limited, and an aqueous solution of sulfuric acid-hydrogen peroxide, ammonium persulfate or sodium persulfate or potassium persulfate can be used. Wait for an aqueous solution of a sulfate solution, ferric chloride or copper trichloride, and the like. (4) The resist pattern peeling process is a resist pattern 5 which is present in a state in which the copper circuit pattern 8 is buried between the copper circuit patterns 8 and can be directly left as an insulating layer without being peeled off, and the mixture is required to be resistant only by an alkaline aqueous solution or a solvent. The etching pattern 5 is swelled and peeled off and/or removed by a so-called degumming treatment using a permanganic acid alkaline salt or the like, and as shown in FIG. 2(D), the wiring board in which only the copper circuit pattern 8 is formed on the substrate 1 is formed. . (5) Interlayer Resin Insulation Layer Forming Process Further, when a multilayer printed wiring board is produced, the substrate having the resist pattern 5 and the copper circuit pattern 8 as shown in the second (C) above, or FIG. 2 (D) The surface of the substrate having only the copper circuit pattern 8 shown, for example, an epoxy resin, a polyimide resin, a cyanate resin, a maleimide resin, a double bond-bonded polyphenylene ether resin, etc. One or two or more kinds of resin compositions such as a bromine-containing or phosphorus-containing compound, and a thermosetting resin composition such as a catalyst, a hardener, or a hardening accelerator which are well-known to be blended, -28-201127238 Coated, heat-hardened, or impregnated with glass fiber, non-woven fabric, woven curable resin composition, semi-cured semi-cured semi-cured laminated film resin, as shown in Figure 3 (A), The grease insulating layer 10 is formed, and the surface thereof is subjected to the treatment as described above for the purpose of blending. In this case, it is preferable to form a resin emulsion of a copolymerized polyimine resin and a polymaleimide compound on one side of a copper foil described in Japanese Laid-Open Patent Publication No. 2007-242975, for example, in the copper foil or the resin composite copper foil. The resin layer of the composite copper foil is laminated with the B layer resin composition layer, the composite shape of the copper layer plate, and secondly, all the copper foil is removed by etching, and the interlayer resin in which the surface of the fine uneven surface of the copper foil is transcribed is insulated at this time. The roughening treatment is not required, and the subsequent process can form a photosensitive resist film having good adhesion on the surface of the interlayer tree layer 1 to obtain a wiring board. Such a copper-clad laminate can be used with conventional copper-clad laminates. Further, a photosensitive resin composition containing the pre-formation component (D) and the pigment (E) is applied onto the surface of the substrate, and the dry film is bonded to the entire surface, and the entire active energy ray is irradiated to cause photohardening and heating. Thermally hardened, an interlayer resin insulating layer 10 can be formed. The resin composition used for the layer B resin composition layer may be blended with various additives in the range of the properties of the original composition, and the polymerizable monomer may be appropriately used, such as an unsaturated polyester. Prepolymers; polybutadiene, maleated butadiene-acrylonitrile copolymer, polychloroprene, butadiene-benzene polymer, polyisoprene, butyl rubber, fluororubber, Natural rubber molecular weight liquid ~ high molecular weight elastic rubber; polyethylene, poly cloth and other hot sheets, or interlaminar tree roughening in the layer containing the layer of the layer of the layer of the layer formed into a layer 10. The grease is insulated and the heat is hardened or, afterwards, the additive is not damaged. Low double propylene such as diene, ethylene co-gel, -29- 201127238 polybutene, poly-4-methylpentene, polystyrene, AS resin, ABS resin, MBS resin, styrene-isoprene Rubber, propylene rubber, core-shell rubber, polyethylene-propylene copolymer, 4-fluorinated ethylene-6-fluorinated ethylene copolymer; polycarbonate, polyphenylene ether, poly High molecular weight prepolymers or oligomers such as hydrazine, polyester, polyphenylene sulfide, etc.: polyurethanes, etc., can be suitably selected. Other, well-known organic or inorganic filling agents, dyes, pigments, tackifiers, slip agents, antifoaming agents, dispersing agents, leveling agents, photosensitizers, flame retardants, gloss agents, polymerization Various additives such as an inhibitor and a rheological property imparting agent can be used in combination as appropriate. In particular, when opening a hole with a carbon dioxide gas, an inorganic filler should be added appropriately for a good hole shape. For example, vermiculite, spheroidal vermiculite, alumina, talc, sintered talc, ash stone, synthetic mica, titanium oxide, aluminum hydroxide, and the like are generally known. The shape of the dip may be any shape such as a needle shape or a spherical shape. (6) Resist pattern forming process As shown in the above-mentioned 3rd (A), the substrate 1 on which the interlayer resin insulating layer 1 is formed is formed as described above, and a photosensitive resist film is formed, and a through hole is formed as needed. After 1 1 , the photosensitive resist film is subjected to selective exposure and development in the same manner as the above-described process (1), and as shown in FIG. 3(B), an electroless copper plating may be formed to form a groove pattern in which a circuit forming portion is formed. A copper plating layer outer layer resist pattern 12 is formed. When the photosensitive resin composition used for forming the photosensitive resist film contains the thermosetting component (D), for example, it is further heated and cured at a temperature of about 140 to 180 ° C to form the carboxyl group-containing resin (A). -30- 201127238 The residue reacts with the thermosetting component (D) having two or more cyclic (sulfur) ether groups in the molecule to form heat resistance, chemical resistance, moisture absorption, and adhesion. A hardened film with excellent properties such as electrical characteristics. Further, when the thermosetting component (D) is not contained, the ethylenic unsaturated bonding of the photocurable component remaining in an unreacted state at the time of exposure may be thermally radically polymerized by heat treatment to enhance the film properties. Therefore, heat treatment (thermosetting) can be performed depending on the purpose and application. (7) Electroless copper plating-electrolytic copper plating process, after the exposed surface of the interlayer resin insulating layer 1 and the entire surface of the resist pattern I2 are the same as the above-mentioned process (2), as shown in Fig. 3(C) As shown in the figure, electroless copper plating is performed, and secondly, until the surface is substantially smooth, electrolytic copper plating is performed to form a copper plating layer 13 covering the outer surface of the resist pattern 12. In this case, the same as the above process (2), Before the copper ore is electrolyzed, the electroless copper plating is formed on the surface of the resist pattern 12, and the resist pattern 12 may be further irradiated with ultraviolet rays stronger than that during exposure or heated to the resist glass. Temperatures above temperature (Tg) or plasma treatment of argon, oxygen, etc. (8) The etching process is as shown in Fig. 3(C), after forming the outer copper plating layer 13, the same as the above process (3), until the surface of the resist pattern 12 is exposed, mechanically honing and/or chemical enthalpy The grinding or etching uniformly reduces the copper plating layer 13 as shown in Fig. 3(D) to expose the outer copper circuit pattern 14 from the surface. The resist pattern 12 existing in the state between the copper circuit patterns 14 can be directly used as an insulating layer without being peeled off, and is only required for an anti-hungry pattern 1 2 with an alkaline aqueous solution or a solvent. The wiring sheet which forms the outer layer copper circuit pattern 14 is formed by swelling and peeling, and/or performing a so-called stripping process and removing it to become a surface layer part. Further, the multilayer printed wiring board can be produced by repeating the above processes (5) to (8) with good productivity. With the circuit pattern formed by the method of the present invention as described above, even when the line and the interval are less than 5 /z m, there is no electric conductor between the circuit patterns, and the circuit is excellent in insulation reliability. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, however, the present invention is not limited to the examples described below. In addition, the following '%' and the like are all based on quality unless otherwise stated. Preparation of photosensitive resist composition; The various components shown in the following Table 1 were blended at a ratio (% by mass) shown in Table 1 below, and pre-mixed by a machine, and then twisted by three rollers. Photosensitive resist composition. -32- 201127238 Table 1 Composition (% by mass) Resist A A resist B Photosensitive resin - I·1 222 Photosensitive resin - 2" 154 Photosensitive polymer 40 20 Photopolymerization initiator Μ 5 5 Thermosetting resin *5 25 pigment paste·6 3 inorganic coating” 70 heat curing catalyst 0. 5 Remarks *1 : CYCLOMERP (ACA) Ζ254 (DAICEL-CYTEC COMPANY LTD. Photosensitive copolymer, solid part 50%, acid 値l〇〇mgKOH/g) *2 : UE-9210 (acid-modified epoxy acrylate manufactured by DIC Corporation, solid portion 65%, acid strontium 80 mgKOH/g) *3 : Trimethylolpropane triacrylate*4 : TPO-L (acyl phosphine oxide photopolymerization initiator manufactured by BASF) *5 : NC-3000 (NIPP〇NKAYAKUCO. ,LTD. Diphenylphenolic epoxy resin) *6 : Indigo blue and propylene glycol methyl ether acetate 1: 9 paste *7 : 矽 gypsum (ADMATECHS globular vermiculite, solid part 70%: propylene glycol methyl ether Acetate solution) *8 : 1B2PZ (Imidazole compound manufactured by Shikoku Kasei Kogyo Co., Ltd.) Preparation of dry film Each of the obtained photosensitive resist compositions was further diluted with propylene glycol methyl ether acetate to obtain 1 OdPa.  S resist solution. It was applied to a film of polyethylene terephthalate having a thickness of 16 Mm by a film coater, and the temperature was gradually raised from 50 ° C to 80 ° C to obtain a resist thickness of 10 //. a dry film of m. The obtained dry film was regarded as dry film A and dry film B, respectively. Example 1 -33- 201127238 The thickness of the insulating layer is 0. 2mm, 12ym two-sided copper foil (copper foil shape 3. 3 A m ) BT resin copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., trade name: CCL-HL830) is used as a copper-clad laminate, and a metal drill bit is used to form a through-hole of the aperture 75 to be degummed (permanganese) The potassium acid-based degumming solution (manufactured by Okuno Pharmaceutical Co., Ltd.) is used to swell, remove (dissolve), neutralize, and wash, and then etch all the copper layer of the surface, and secondly, use a vacuum laminating machine manufactured by NICHIGO-MORTON Co., Ltd. The dry film A was bonded to the conditions of 7〇〇c, 〇5Mpa, and 3〇 seconds. Thereafter, it was irradiated under the condition of 1 〇〇mJ/cm2 by a laser direct exposure apparatus (param0n manufactured by ORBOTECH Co., Ltd.). 5 5nm ultraviolet rays 'depicted the minimum line and the interval is 10 private m pattern. Thereafter, using a 1 wt% sodium carbonate aqueous solution at 30 ° C, the development is carried out at a pressure of 2 atmospheres, and the water washing is repeated twice to obtain a photosensitive film. The substrate of the resist pattern was subjected to UV curing under the conditions of 300 mJ/cm 2 by a UV conveyor belt device equipped with a high-pressure mercury lamp, and then subjected to plasma treatment under conditions of 500 W, 250 mTorr, and 60 seconds using oxygen plasma. Electroless copper plating solution (Okuno Pharmaceutical Co., Ltd.) ATS ADD COPPER CT) Electroless copper plating is carried out to form a copper layer with a thickness of l#m. After heating for 2 hours in a heating furnace at 30 ° C, a copper sulfate plating solution is used. 5 amps/dm2 was subjected to electrolytic plating for 70 minutes to form a copper layer of about 10/zm thick. The substrate on which the copper layer was formed was etched with an etching solution (SE-07, manufactured by Gas Chemicals Co., Ltd.) to etch the copper foil to make it flat. The substrate on which the circuit is formed is peeled off by an alkaline stripping solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., R-200) at 50 ° C, 3 minutes - 34 - 201127238, and the photosensitive process is completely removed by a stripping process. Scratch, get the minimum line and the circuit board with a spacing of 1 ο // m. Example 2 The circuit board obtained in Example 1 was subjected to CZ treatment by EC, and a layer of a resin layer containing a copper foil (a copper foil profile of 3 · 3 m) was attached (Mitsubishi Gas Chemical Co., Ltd. ), CRS - 4 0 1 ) is applied to both sides, heating conditions: 110 ° C x 30 minutes + 180 ° C x 90 minutes, pressurization conditions: 5 kgf / cm 2 x 1 5 points + 20 kgf / cm 2 'In the final condition, vacuum 3 〇 Below the mmHg, the layer was formed in a two hour condition. The surface copper foil of the 4-layered plate obtained by etching was irradiated with a carbon dioxide gas laser (output of 13 mJ) to form a blind hole having a pore diameter of 6 0 /z m. Then, the dry film a was bonded under the above-described conditions, and the circuit was formed in the same manner as in the first embodiment, and a four-layer circuit substrate having a minimum line and a space of 10 mm was obtained. [Example 3] In the case of Example 1, the dry film A was replaced with a dry film B, and the copper layer of the copper foil layer which was entirely etched on the surface was bonded, and thereafter, a laser direct exposure apparatus (ArBOTECH, Paragon, Inc.) was used in the same manner. The ultraviolet rays of 355 nm were irradiated under the conditions of 200 mJ/cm2, and the pattern of the minimum line and the interval of 20 μm was drawn. Thereafter, development was carried out at a pressure of 2 atm using a 1 wt% aqueous sodium carbonate solution at 30 ° C, and water washing was repeated twice to obtain a substrate on which a photosensitive resist pattern was formed. After curing in a hot air drying oven at 150 ° C for 1 hour, the electric hair treatment was carried out under the conditions of -35 - 201127238 500 w, 250 mTorr, and 60 seconds. Next, electroless copper plating was performed using an electroless copper plating solution (ATS ADD COPPER CT) to form a copper layer having a thickness of i#m, and heating was performed for 2 hours in a heating furnace at 130 °C. , using copper sulfate plating solution to 1. 5 amps/dm2 was subjected to electrolytic copper plating for 70 minutes to form a copper layer of about thick thickness. The substrate on which the copper layer was formed was etched (Mitsubishi Gas Chemical Co., Ltd., SE-07) until the surface of the dry film was visible, and the copper foil was etched to be flat, and the minimum line and interval were 20. ^ m circuit board. [Example 4] The circuit board obtained in Example 3 was subjected to a CZ treatment by MEC Co., Ltd., and after the adhesion treatment, the dry film B was bonded thereto in the same manner as in Example 1, and the solder resist pattern was exposed and developed. After that, a hot air drying oven was used to perform heat curing at 150 ° C for one hour to obtain a circuit board on which a solder resist layer was formed. Example 5 After performing a CZ treatment on a four-layer circuit board obtained in Example 2, the same procedure as in Example 1 identical, fit dry film solder mask (TAIYO INK MFG. CO. , LTD. , AUS410, film thickness 20#m), after exposure and development of the solder resist pattern using a high-pressure mercury lamp at 600 mJ/cm2, and then hot-drying at 150 ° C for 1 hour using a hot air drying oven A circuit board with a solder mask. -36- 201127238 Comparative Example 1 The insulation layer is thick. 2mm, 12// m double-sided copper foil (copper foil shape 3. 3 Vm) BT resin copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., trade name CCL-HL8 3 0 ) is used as a copper-clad laminate, using a metal drill to form a through hole with a hole diameter of 75 # m, and secondly, an etching solution (Mitsubishi Gas Chemical Co., Ltd., SE-〇7) etches the copper foil layer on the surface to a flat surface. 0"m, after degumming treatment (potassium permanganate-based degumming solution (made by Okuno Pharmaceutical Co., Ltd.) for swelling, degumming (dissolving), neutralizing, and washing, electroless copper plating is formed. 1 # m of the copper layer, followed by the implementation of 1 30 ° C, 2 hours of heat treatment 'Second, using NICHIGO-MORTON company vacuum laminator to 7 ° ° C, 〇. 5Mpa '3 sec. conditions for the semi-additive dry film (Hitachi Chemical Co., Ltd., RY-3515). Thereafter, ultraviolet rays were irradiated under conditions of 100 mJ/cm 2 using an ultraviolet exposure apparatus (manufactured by Bodo Co., Ltd., HAP-5 020) to draw a pattern of minimum lines and intervals of 10 // m. Thereafter, development was carried out by using a lwt% sodium carbonate aqueous solution at 30 °C under a spray pressure of 2 atm, and the water washing was repeated twice to obtain a substrate on which a photosensitive resist pattern was formed. Secondly, use copper sulphate plating solution to 1. 5 amps/dm2 was subjected to electrolytic copper plating for 70 minutes, and a copper pattern of about 10#ιη thick was formed on the portion where the resist layer was not formed. Next, an alkali stripping solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., R - 2 0 0) was used, and 50 was used. (:, a condition of 3 minutes, after peeling off a half-size dry film, an etching solution (made by Mitsubishi Gas Chemical Co., Ltd., SE-07) was used, and the substrate on which the copper pattern was formed was semi-added. Before the film portion disappeared, the copper circuit was etched to obtain a circuit board having a minimum line and a spacing of 10 m. -37- 201127238 Comparative Example 2 After the CZ process of MEC Co., Ltd. was performed on the circuit board produced in Comparative Example 1 Hardening dry film (Ajinomoto Fine-Techno Co. , Inc. The system 'ABF-GX13' is attached to both sides, using a vacuum laminating machine made by NICHIGO-MORTON Co., Ltd. at 7 °C, 〇. After bonding at a condition of 5 MPa and 30 seconds, the layer was formed by hot-hardening at 170 ° C for 60 minutes using a hot air drying oven. The obtained substrate was irradiated with a carbon dioxide gas (output of 13 mJ) in one shot to form a pupil having a pore diameter of 60 // m. Next, the gel removal treatment (potassium permanganate-based degumming solution (manufactured by Japan MacDermid Co., Ltd.) is used to swell, remove (dissolve), neutralize, remove the smear of the pupil, and perform hardening of the heat-hardened dry film. Concave and convex treatment of the surface. At this time, the unevenness of the surface of the resin is Rz5. 3 μπι. On the substrate, an electroless copper plating solution (ATS ADD COPPER CT) was used to form an electroless copper shovel to form a copper layer having a thickness of 1 jam, and the mixture was heated in a heating furnace at 130 ° C for 2 hours. Using a vacuum laminator made by NICHIGO-MORTON Co., Ltd. at 70 ° C, 0. A dry film is applied to a half-added amount of 5 Mpa and 30 seconds. Thereafter, ultraviolet rays were irradiated under the conditions of 100 nU/cm 2 using an ultraviolet exposure apparatus (manufactured by OC Corporation), and a pattern of a minimum line and an interval of 1 〇 Μ m was drawn. Thereafter, development was carried out using a 1 w t % sodium carbonate aqueous solution at 30 ° C at a spray pressure of 2 atm, and the water washing was repeated twice to obtain a substrate on which a photosensitive resist pattern was formed. Next, using a copper sulfate plating solution for the substrate, 1. 5 amps/dm2 was subjected to electrolytic copper ore for 70 minutes, and a copper pattern of about 10//m thick was formed in the portion where the resist layer was formed. Next, using an alkaline stripping solution (Mitsubishi Gas Chemical Co., Ltd., R-200), peeling the semi-added dry film at 50 ° C for 3 minutes, using a contact engraving solution -38- 201127238 (Mitsubishi Gas Chemicals Co., Ltd., SE-07) etching a copper circuit until the copper portion of the substrate on which the copper pattern is formed forms a semi-added dry film disappears, and a multilayer having a minimum line and a spacing of 1 〇β m is obtained. Circuit board. Further, on the substrate, a dry film solder resist layer (TAIYO INK MFG.) was formed in the same manner as in Example 5. CO. , LTD. The solder resist pattern of the system, AUS410), obtains a substrate on which the solder resist layer is formed. The circuit board produced in each of the above examples and comparative examples was subjected to a characteristic test as described later. The results are shown in Table 2. Table 2

Characteristic Example Comparative Example 1 2 3 4 5 1 2 Peel strength (N/cm) 9.3 10.1 8.9 9.2 9.8 7.8 5.9 Solder heat resistance 〇〇〇〇〇〇〇 Thin line forming 〇〇〇〇〇X Δ Electroless plating suitability 〇〇〇〇〇〇X (1) Peel strength According to JIS C 6 4 8 1, the average enthalpy of the peel strength measured three times. (2) Solder heat resistance was treated at 1 2 1 ° C and 2 0 3 kP a for 4 hours, and then immersed in a soldering night at 260 ° C for 30 seconds to observe whether there was an abnormality such as circuit peeling or resin peeling. The evaluation is based on the following criteria. 〇: Abnormal X: Partial expansion (3) Thin line formation -39- 201127238 Observed by microscope observation whether L/S (line/space) = 1 〇/1 〇am or L/S = 2 0/2〇em Thin lines are evaluated on the basis of the following criteria. 〇: Formed without problems. A: A very small part was found to be peeled off. X: visible peeling. (4) Electroless plating suitability Electroless nickel plating was applied to each wiring board, and electroless plating was performed to confirm whether or not the etching residue at the time of circuit formation caused abnormal precipitation of the plating, and was evaluated according to the following criteria. 〇: No abnormal precipitation. X: Electroplating is performed on a resin without wiring. As a result of the results shown in Table 2, in the first to fifth embodiments, the wiring board formed a circuit in a state in which the surface of the copper foil had a surface roughness by etching all of the copper foil, and as a result, the peel strength was high. Further, a layer (electroconducting layer) of electrolytic copper plating is formed on the entire surface of the substrate and the photosensitive resist film by electroless copper plating, and then, after the electrolytic copper plating layer is formed in total, the surface of the photosensitive anti-crack film is exposed. The flat wiring is etched, and the formed wiring board has high definition, because there is no trace of the formation of the conductive layer between the completed circuits, and there is no possibility of abnormal precipitation of nickel and plating due to poor etching. Further, in the wiring board obtained in the third embodiment and the fourth embodiment, the circuit and the insulating layer are flat, and the solder resist layer can be formed to have a uniform film thickness, which is a method of forming a high precision. On the other hand, in the case of Comparative Example 1, as in the case of the embodiment, the copper foil of the wiring board was entirely etched, and in the case where the surface of the copper foil had a thickness, the circuit was formed in the case of -40 to 201127238, so that the peeling strength was relatively high. the result of. However, since the base resin is large in appearance, the fine line separation caused by the overetching when the copper foil layer is peeled off can be seen. On the other hand, in Comparative Example 2, the unevenness of the copper foil was not used and the unevenness was formed on the resin by the stripping process, so that the peeling strength of the completed circuit was lower than that of the examples. Further, in the case of electroless nickel plating or electroless plating which is processed after forming the wiring board, plating on the resin other than the wiring is also abnormally deposited by plating. It should be because an electroless copper shovel is formed between the thin wires (below the photosensitive resist film), and even if etching is performed, palladium of the catalyst for electroless copper plating is not etched and remains. The method for producing a printed wiring board of the present invention is suitable for producing a high-density printed wiring board and a multi-layer printed wiring board having a highly precise and extremely fine copper circuit pattern on the surface of the substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic partial cross-sectional view showing a preferred embodiment of a process for forming a photosensitive resist film on a substrate surface. 2 is a printing process of the present invention including a groove pattern forming process for a photosensitive resist film formed on a surface of a substrate, an electroless copper plating-electrolytic copper plating process, an overall honing or etching process, and a resist peeling process. A cross-sectional view of an embodiment of a method of manufacturing a wiring board. Fig. 3 is a schematic partial cross-sectional view showing an embodiment of a method of manufacturing a printed wiring board according to the process of forming a printed wiring board according to the present invention from the formation of a resin insulating layer to the formation of a copper circuit pattern. -41 - 201127238 [Description of main component symbols] 1 : Substrate 2 : Copper foil 3 : Copper-clad laminate 4 : Photosensitive resist film 5 : Anti-contact pattern 6 : Through hole 7 : Mineral copper layer 8 : Copper circuit pattern 9 : plating through hole 1 〇: interlayer resin insulating layer 1 1 : through hole 1 2 : outer layer resist pattern 1 3 : outer layer copper plating layer 14: outer layer copper circuit pattern - 42

Claims (1)

201127238 VII. Patent application scope: 1 . A method for manufacturing a printed wiring board, comprising: (a) selectively exposing and developing a photosensitive resist film formed on a surface of a substrate to form a circuit formed. a portion of the groove pattern may be formed by electroless copper plating to form a patterned resist film of the copper plating layer; (b) performing electroless copper plating on the exposed surface of the substrate of the groove pattern portion and the entire surface of the patterned resist film Secondly, a process of forming an electrolytic copper plating to form a copper plating layer to cover the resist film until the surface is substantially smooth; and (c) mechanically honing and/or chemical enthalpy until the surface of the resist film is exposed. Grinding or etching processes that uniformly reduce the copper plating layer to expose the copper circuit pattern from the surface. 2. The method according to claim 1, wherein after the process (c), the process of removing the resist film by the surface layer portion only as a copper circuit pattern is further included. The method according to the first aspect of the invention, wherein the substrate has a surface on which the copper foil of the copper-clad laminate is etched and the surface of the copper foil is transcribed. 4. The method according to claim 1, wherein the resist film is formed by patterning, and at least one selected from the group consisting of ultraviolet irradiation, heat treatment, and plasma treatment is performed. One type of treatment 'can be formed by electroless copper plating to form a copper plating layer. 5. The method according to claim 1, wherein in the process (a), the photosensitive resist-43-201127238 film formed on the surface of the substrate is subjected to ultraviolet light pattern exposure or direct ultraviolet light drawing. The exposure is followed by "development" to form a groove pattern of the circuit forming portion. 6. The method according to claim 2, wherein in the process (d), the resist film is removed by an alkaline aqueous solution or by a degumming treatment. The method according to the first aspect of the invention, wherein the substrate used in the process (a) has a through hole. 8. The method according to claim 1, wherein the process (c) is followed by forming a photosensitive resist film after forming the interlayer resin insulating layer, and secondly, repeating the processes (a) and (b) And (c) to produce a multilayer printed wiring board. 9. The method according to claim 2, wherein after the process (d), a photosensitive resist film is further formed after forming the interlayer resin insulating layer, and then the processes (a) and (b) are repeated. (c) To produce a multilayer printed wiring board. 10. The method of claim 8, wherein after repeating the processes (a), (b), and (c), further performing the foregoing (d) in such a manner that the surface layer portion is only a copper circuit pattern. The resist film removal process. 1 1. The method according to claim 9, wherein after repeating the processes (a), (b) and (c), the surface layer portion is further embodied as a copper circuit pattern (d) The resist film is removed from the process. 1 2. A printed wiring board, which is characterized in that: - 44 - 201127238 has a copper circuit which is formed by the method described in any one of the above-mentioned claims 1 or 3 to 9 and which is buried in the surface layer portion. A resin insulating layer between the pattern and the pattern forms a flat surface with the copper circuit pattern and the resin insulating layer. -45-