TW200945980A - Manufacturing method for circuit wiring board - Google Patents

Abstract

A manufacturing method for a circuit wiring board includes the steps of: forming (S1) a coating film by applying a coating liquid containing a polyimide precursor resin and a metallic compound onto a base; forming (S2) a resist mask into a pattern on the surface of the coating film; forming (S3) a metal deposition layer by reducing metal ions present in the coating film; forming (S4) circuit wiring having a pattern by plating on the metal deposition layer; and forming (S5) a polyimide resin layer by imidizing a layer of the polyimide precursor resin by heat treatment.

Description

200945980 VI. Description of the Invention: [Technology of the invention] The invention relates to the use of electronic components, and in particular, the circuit wiring formed by the manufacturing route of the fiber-reinforced polyimide substrate The manufacturing method of the substrate and the formation of a patterned electric system [Prior Art] In the electronic circuit of the electronic device, the surface of the substrate (and the inside of the insulating substrate) which is used for circuit processing of the laminated board formed by the laminated board and the conductive material is used. The printed circuit board is printed on the conductor pattern, and the insulator tree is used as the substrate. / According to the electrical design = rigid printed wiring board with plate shape and soft type:: wiring board. The flexible printed wiring board is characterized in that the flexible portion of the flexural bending is ~...flexible 'in the case of the regular printed wiring board can be in the electric == and (4) the flexibility is saved in the state of the second door. It can be used as a wiring material for the interlayer. As a material of the flexible printed wiring board, an insulating resin such as polyimide or polyimide can be used as a material for heat-resistant polyimide. Imine In addition, the amount of grease is an absolute amount. In other respects, the conductivity of the conductive material is usually made of copper foil. In recent years, 'the miniaturization of electronic components and the speed of signal transmission speed are on the circuit of flexible printed circuit boards. A fine fine space and a gas path are required in the substrate. As a method of forming a fine fine pitch line, a known method such as a vapor deposition method and a sputtering method, but a metal crucible formed by such a method, 098104040 200945980 The deviation from the (four) degree of the polyamidene resin substrate is large, or pinholes are easily generated, and further, in the above method, since the package is processed, the polyimide resin base is used. If the material is not on the layer 2 (4)), the removal will be shaken, the __ bribe __ over-etching concerns. ❹ ❹ In recent years, as a method for maintaining a relatively good adhesion between a polyimide substrate and a metal gland, a method that has been proposed is, for example, a direct metallization ( Direet MetalizatiQn) Method The metal film of the method (4), which is partially embedded in the resin towel of the polyimide substrate, can be left with high density. Direct metallization of the limbs, not (4) treatment. For example, in Patent Document 2, it has been revealed that in the case where the surface axis of the polyanilin resin substrate is miscellaneous, the (10) solution is supplied to the microfluidic path to form a modified surface on the surface of the polyimide resin substrate. After the layer, metal ions are brought into contact with the reforming layer to reduce the metal ions to form a metal ruthenium. On the other hand, in Patent Document 3, a method of selectively causing a hydrophobic substance to adhere to a surface of a polyimide to selectively expose the exposed portion thereof is disclosed. Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-73159. Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-103479 (Patent Document No. 2007-242689) SUMMARY OF INVENTION (Problems to be Solved by the Invention) 098104040 5 200945980 However, as in the case of the invention of Patent Document 2, when a pattern forming method for forming a micro flow path is used, as a mask material for forming a micro flow path groove, an alkali-resistant material must be selected, and the material selection is not Easy, is the problem. Further, in the method of Patent Document 2, in order to improve the accuracy of the rain pattern, it is necessary to have a high dimensional accuracy in the processing of the mask material, which is a problem. In particular, if the adhesion precision of the contact portion of the polyimide substrate and the mask = is low, a gap is formed between the two, and the treatment liquid such as the metal ion solution or the reducing solution may ooze out there. Therefore, there is a concern that the accuracy of the pattern is lowered and the electrical characteristics of the circuit are adversely affected. Specialized in the θ species of the literature 3, in order to adhere to the surface of the poly-imine to dissolve the hydrophobic substance in the aqueous solution, it must be treated with plasma, and it is necessary to treat the Xf biomass. . Further, in the invention of Patent Document 3, before the adhesion of the hydrophobic 1± substance, the mask layer must be formed by photolithography to have a step of removing the mask layer after adhesion. This means that in order to (4) form a pattern for the hydrophobic substance of the mask, it must be shaped; the mask is masked and stripped, and the number of steps is extremely complicated and complicated, which is the problem. 'Providing a method for simplifying the complicated manufacturing steps in the past = a method of manufacturing a circuit board having a fine fine pitch and having a circuit wiring and an insulating resin layer in close contact with each other. (Means for Solving the Problem) The method for manufacturing a circuit wiring board of the month is a method for manufacturing a circuit wiring board formed by forming a circuit wiring on a polyimide film layer 098104040 200945980, and is characterized in that the following steps are provided : a) a step of forming a coating film by applying a coating liquid containing a pro-imine precursor resin (precursor of a poly-bromide resin) and a metal compound on a substrate to dry it; b) a step of coating the surface of the coating film with a photoresist layer to form a photoresist mask; ❹ reducing the metal ions in the coated crucible to precipitate the metal on the surface of the coating film a step of forming a metal deposition layer not in the region covered by the photoresist mask; d) a step of forming a patterned circuit wiring by electroless ore and/or electric ore on the metal deposition layer; e) a step of forming the above-mentioned polyimine resin layer by subjecting the polyimine precursor resin layer in the above coating film to heat treatment by heat treatment. Further, in the method for producing a circuit board of the present invention, after the step a), further comprising: f) drying the coating film with a metal ion-containing aqueous solution to make the coating The step of increasing the metal ion content; or after the step a), further comprising: g) applying the ammonia solution to the coating film described above or! A step of impregnation of an aqueous solution of a primary or secondary amine. (Effect of the Invention) According to the method for manufacturing a circuit material substrate of the present invention, since the silver etching step of the seed layer (metal deposition layer) is not required, the simple steps of 098104040 7 200945980 can be simplified to form fine fineness. Since the pitch circuit is used, it is not necessary to provide a large-scale capital supply, and the circuit wiring and the insulating resin layer can be manufactured (the polyimine tree L is densely packed with a circuit board, so the industrial value is very high. Others of the present invention The purpose, the features, and the advantages of the present invention will be fully described below with reference to the drawings and FIG. 2 as an embodiment of the present invention. FIG. 2 is an explanatory diagram of the steps of the main steps of the method of manufacturing the wiring board; FIG. 2 is an explanatory diagram of each step. The circuit wiring board 1 (?) obtained by the manufacturing method of the present invention is, for example, as shown in FIG. 2(e) The structure of the polyimine resin layer 3 is formed by forming the circuit wiring 9. The form of the polyimine resin layer 3 is not particularly limited, and for example, it may be a film of a polyimide film. In addition, the substrate 1 may be in the form of a metal foil, a glass plate, or a substrate 1 such as a film. Further, as the substrate 1, a sheet-like layer in which a polyimide layer 3 is laminated may be mentioned. a resin, a glass substrate, a ceramic, a metal foil, etc. Further, the substrate 1 may be made of a polyimide resin. The entire thickness of the polyimide layer 3 may be set to be in the range of 3 to 1 Å/m. 'It is preferably in the range of 3 to 50. The polyimine resin can be formed by imidating (hardening) the polyimine precursor resin quinone, here, the term "polyimine precursor resin" Also included is a light-emitting group (for example, an ethylenically unsaturated hydrocarbon group) in the molecular skeleton of 098104040 8 200945980. Details of the oxime imidization will be described later. [Step a: Coating film forming step] In the present embodiment In the method for producing a circuit board, the coating liquid containing the polyimide precursor resin and the metal compound is applied onto the substrate 1 and dried, as shown in FIGS. 1 and 2(a). The coating film 3a is formed as it is (step S1). As a polyimide precursor resin (hereinafter also referred to as "only" In the case of the precursor, a precursor of a known polyimine which can be obtained by using a known acid anhydride and a diamine can be produced by a known method. The precursor, for example, can be a tetra-baric acid dianhydride and a diamine. The solvent is substantially dissolved in an organic solvent, and stirred at a temperature in the range of 〇100 ° C for 30 minutes to 24 hours, and then subjected to polymerization reaction. The reaction can be used to make the precursor in an organic solvent. The reaction component is dissolved in a range of 5 to 30% by weight (preferably in the range of 1 Torr to 20% by weight). The organic solvent used in the polymerization reaction is preferably used as an organic polar solvent. For example, N,N-didecylamine, N,N-dimercaptoacetamide (DMAc), N~mercapto-2-pyrrolidine, 2-butanone, disulfoxide, Dimethyl sulphate, cyclohexanyl, dioxane, tetrahydrofurazan, m trisuccinyl ether, and the like. These solvents may be used in combination of two or more kinds, and in addition, aromatic hydrocarbons such as diphenylbenzene and hydrazine may be partially used. The precursor of the synthesis can be used as a solution state. Usually, it is preferably used as a reaction solvent solution, and if necessary, it may be concentrated, diluted or substituted with another solvent. Also, since the precursor is generally excellent in solvent solubility, it can be advantageously used in 098104040 9 200945980. The solution thus adjusted can be utilized as a coating liquid by adding a metal compound. The precursor is preferably selected to contain a thermoplastic polyimine resin after imidization. By using a thermoplastic resin, the adhesion to the metal deposition layer 7 (described later) can be improved. Such a thermoplastic polyimine resin preferably has a glass transition temperature of 350 ° C or less, more preferably 200 to 320 ° C. As a precursor of the thermoplastic polyimine resin, a divalent aromatic group represented by the formula (2)' = (3) or (4) in the formula (1) is used as a precursor of the structural unit represented by the following (1), An Representing = aromatic group 'in formula (2) to formula (4), R, Table 2) 6 is a sulphate-based oxy group, n is an independent singularity of 4 carbon _ 立立单键 or selected from 3) Broad,, or - the valence of 2 in the side. The presence of the two digits is in the range of 0.1 to 1.0. Early [Chemical 1]

In the above formula (1), An may be referred to as a residue of a diamine, and »〇C.(8) Ar2 may be referred to as a residue of an acid anhydride 098104040 200945980'. Therefore, a preferred polyimine resin may be a diamine and an acid anhydride. To explain. However, the term "thermoplastic polyimine resin precursor" is not limited to those obtained by this method. Preferred diamines which are suitable for the preparation of the precursor of the thermoplastic polyimine resin include, for example, 4,4'-diaminodiphenyl ether and 2,_decyloxy-4,4. ,-diaminophenylaniline, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 2, 2_bis[4-(4- Aminophenoxy)phenyl]propane, 2,2'-dimercapto-4,4,-diaminobiphenyl, 3,3'-dihydroxy-4,4,-diaminobiphenyl , 4, 4'-diaminobenzidine and the like. Further, it is also exemplified in the description of the low thermal expansion polyimine resin described later. Among these, as a particularly preferred diamine component, it is selected from the group consisting of 1,3-bis(4-aminophenoxy)-2,2-dimercaptopropane (DANPG), 2, 2-double [4-(4-Aminophenoxy)phenyl]propane (BAPP), 1, 3-bis(3-aminophenoxy)benzene (APB), p-phenylenediamine (p-PDA), 3 One or more kinds of diamines of 4'-diaminodiphenyl ether (DAPE34) and 4,4'-diamino hydrazine diphenyl ether (DAPE44). The acid anhydride used in the preparation of a precursor suitable for use in the thermoplastic polyimide resin may be, for example, pyromellitic anhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride. , 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-oxydiphenyl phthalic anhydride. Further, the acid anhydride described in the description of the low thermal expansion polyimide resin described later can be used. Among these, as a particularly preferred acid anhydride, it is selected from the group consisting of pyromellitic anhydride (PMDA), 3,3', 4, 4'-biphenyltetracarboxylic dianhydride (BPDA), and 3,3'. , 4,4'-diphenyl ketone tetracarboxylic dianhydride 098104040 11 200945980 (BTDA), 3'3,4,4'-biphenyl turned over (tetra) two Xuan (with) anhydride. The diamine 'anhydride can be used alone or in combination. Further, diamines and acid anhydrides other than the above may be used in combination. The precursor of the thermoplastic polyimine resin is represented by the above formula (1) = structural unit, may be present in homopolymer (IV), or may be present in the structural position of the copolymer. In the case of a copolymer having a plurality of structural units, it may be in the form of a block copolymer or may be in the form of a random copolymer. The structural unit represented by the formula (1) is plural, but may be one type or two or more types. Preferably, the structural unit represented by the formula (1) is used as a main component, and more preferably a precursor containing (tetra) mol% or more (more preferably 8 Gmol% or more). In the present embodiment, in order to prepare a coating liquid, a commercially available product may be used as a solvent containing a precursor. For example, Nippon Steel Chemical Co., Ltd. (8) Thermoplastic Polyimine Precursor Resin Varnish spi_2 〇 商品 商品 = = = = = = = = = = = = = = = = = = = = = = = = = = = ( = ( ( ( ( ( ( ( ( ( Toraynish #3000 (trade name) and so on. a metal compound containing a metal compound contained in the (IV) liquid as a precursor, and a metal species having a redox potential higher than that of the reducing agent used in the reduction treatment (described later) in the precipitation layer 7 and Yite:] All restrictions can be used. As the metal compound, it is possible to include a correction. d, Ag, AU, Pt, such as, Fe, C. Metals such as Cr, Rh, Ru, etc.

Inside. As the metal compound, it is possible to use a metal salt or an organic carbonyl group of 098,040,040, ❹ ❹ 12 200945980. The salt of the metal may, for example, be a hydrochloride, a sulfate, an acetate, an oxalate or a citrate. As the metal salt, the above metal can be preferably used. It is Cu, Nl, or Pd. x ' as an organic group-based compound which can form an organic base group with the above-mentioned metal, and examples thereof include: bis(b) fluorene, benzene f propylene phthalocyanine, benzophenone carbaryl, etc. Stuffed with acetic acid, such as ethyl vinegar, etc. - oxocarboxylate. Preferable specific examples of the metal compound include Ni(CH3C00)2, ❹Cu(CH3COO)2, Pd(CH3C00)2, NiS〇4, CuS〇4, PdS〇4, NiC〇3, CuC〇3. , PdC〇3, N1CI2, C11CI2, PdCl2, NiBn, CuBr2, PdBr2

Ni(N〇3)2, NiC2〇4, Ni(MO2)2, Cu(NH4)2C14, Cul, Cu(N〇3)2, Pd(N〇3)2, Ni(CH3C0CH2C0CH3)2, Cu( CH3COCH2C〇CH3)2, Pd(CH3C0CH2C0CH3)2, and the like. In the coating liquid containing the precursor and the metal compound, a three-dimensional cross-linking is formed between the metal ion generated by dissociation of the metal compound and the precursor to form a reaction, so that the coating liquid is thickened over time. - Gelation proceeds, making coating of the substrate 1 difficult. In order to prevent such adhesion and gelation, it is preferred to add a viscosity adjusting agent as a stabilizer to the coating liquid. By the addition of the viscosity modifier, the metal ions in the coating liquid form a chelate misalignment with the viscosity modifier instead of forming a chelate complex with the precursor. In this way, by adjusting the viscosity #1, the formation of the precursor and the metal ions can be hindered, and the three-dimensional crosslinking can inhibit the adhesion and gelation. As a viscosity modifier, 曰 on low molecular organic organic compounds with high reactivity with metal ions (ie, 098104040 13 200945980 v metal complex) The range of 50 to 300 is better. As a specific example of the agent, it is possible to adjust the viscosity of the mountain by adding 1 · 乍 for the specific viscosity, for example, ethyl acetonide, B biting, microphone biting, methyl material, and the like. Moreover, the viscosity adjustment: B 曰 曰 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 W W W W W W W W W And the total weight fraction of the viscosity modifier is set to 5 = 4 in the range of material = metal = 10 to 4. The range of parts by weight is preferred. The reason is that the amount is as follows: if the amount of the metal compound is less than 5 parts by weight, the thickness of the metal ion on the surface of the resin layer of the yammine precursor is reduced by the reduction treatment, resulting in uneven thickness of the conductor, such as electroless ore. If more than a part by weight of the metal salt that cannot be dissolved in the cloth liquid will precipitate. Further, as the optional component other than the above components, the "coating liquid" may be, for example, a smoothing agent, an antifoaming agent, a tackifier, a crosslinking agent or the like. The method of applying the coating liquid to the substrate 1 is not particularly limited, and it can be applied by a coater such as a comma type, a mold type, a knife type, or a lip type. Further, the coating liquid is applied onto the substrate 1, and then dried to form a coating film 3a. In the drying, the temperature is controlled in such a manner that the imidization by the progress of the dehydration ring closure of the precursor is not finalized. The method of drying is not particularly limited, and for example, it may be 60 to 200. (: The time in the range of 丨~60 minutes under the temperature condition within the range, preferably, the temperature is 098104040 200945980 degrees in the range of 6〇~15〇乞. The state of the residual precursor, It is necessary to impregnate the aqueous solution containing metal ions. The layer of the precursor after drying may be imidized by one of the precursor structures, but the imidization ratio is preferably 50/min. 'Belows less than 20%), the precursor structure should be more than 5% by weight and the yttrium imidization rate of sodium drive can be obtained by F傅urier conversion-infrared spectrophotometer (commercially available) Product: FT/IR62() of Japan Spectrophotometer) The infrared absorption spectrum of the polyimide film was measured by the transmission method, and the absorbance from the quinone imine group of UL1 was determined by using the benzene® ring hydrocarbon bond of the surface (10)]. Calculated. The coating film 3a may be a single layer or a laminated structure formed of a plurality of coating films. In the case of a plurality of precursors, other precursors may be sequentially applied to the precursor layer formed of different constituent components. The precursor having the same composition of three or more layers of the precursor layer may be used twice or more. The two-layer or single-layer' of the layer structure solution, especially the single layer, is preferred because of the industry. Further, the thickness of the coating medium 3a (after drying) is preferably in the range of 3::, preferably in the range of 3 to Fan. It is preferable to form a coating containing a plurality of layers to contain a metal = material, and it is preferable to use only a part of the compound. The transition of the layer (4) contains the metal in the case where the coating layer 3a is formed of a plurality of layers, and the polyimide layer 3 is formed so that the precursor layer is adjacent to the circuit wiring 9 after the imidization of 098104040 15 200945980 described later. It is preferred that the thermoplastic polyimide layer is a thermoplastic resin layer. Further, at least one of the plurality of layers is preferably such that the precursor layer is formed into a polyiimide resin having a low thermal expansion property after imidization. When such a low thermal expansion polyimide resin is used as the insulating resin layer, it is possible to suppress the warpage of the circuit wiring board, which is advantageous. When the polyimine resin layer is composed of a low thermal expansion polyimide resin layer and a thermoplastic resin layer, the total thickness is 1/2 or more (more preferably 2/3 to 9/10). The heat-expandable polyimine resin layer is preferably formed. Further, in consideration of heat resistance and dimensional stability, the thickness of one layer of the thermoplastic polyimide film layer is preferably 5 / / m or less, preferably in the range of 1 to 4 in m. The linear thermal expansion coefficient of the entire polyimide resin layer is preferably 3〇χ1 (Γ6(1/κ) or less, preferably in the range of 5xl〇-6~25xl〇-6 (l/K). Low thermal expansion poly The quinone imine resin, specifically, has a linear thermal expansion coefficient of lxl (T6 to 30xl -6 (l/K) in the range of 1 χ 1 〇 6 to 25 χ 1 〇 6 (1/κ). Preferably, α 15xl (T6~25χ1 (better in the range of Γ6(1/Κ)) is a low thermal expansion polyurethane resin. The low thermal expansion polyimine resin has the following The polyimine resin of the structural unit represented by the formula (7) is preferred. In the formula (7), An represents a tetravalent aromatic group 'An represented by the formula (8) or the formula (9), and represents an Or a divalent aromatic group represented by the formula (1)), wherein it is an independently monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and v and γ represent an independent single bond or a divalent hydrocarbon group having 1 to 15 carbon atoms; a divalent group selected from 〇, s, c〇, s〇, s〇2, or C0NH, m represents an integer of 〇4, and q represents the presence of a molar ratio of the constituent unit, which is ^丨~^ Scope 098104040 16 200945980 [Chemical 2]

Person Y N-Ar4 - ...(7)

The above structural unit may be present in the homopolymer or in the structural unit of the copolymer. In the case of a copolymer having a plurality of structural units, it may be present as a block copolymer or as a random copolymer. In the above formula (7), An can be said to be a residue of a diamine, and Ar4 can be said to be a residue of an acid anhydride. The preferred polyimine resin is described by a diamine and an acid anhydride. However, the low thermal expansion polyimine resin is not limited to those obtained by this method. The acid anhydride used for the formation of the low thermal expansion polyimine resin layer is preferably exemplified by pyromellitic anhydride, 3,3', 4, 4'-biphenyltetracarboxylic dianhydride, and 3. 3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride. Further, as the acid anhydride, preferred examples are: 2,2',3,3'-, 2,3,3',4'- or 3,3',4,4'-diphenyl ketone four Carboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4' - Diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) 098104040 17 200945980 Ether dianhydride or the like. Further, as _, preferred examples are also: 3,3^,4,r - ^2,3,3^,r 2 r 3>3„carboxylic acid dianhydride, 2,2-double (2 '3- or 3,4_dicarboxyphenyl)-propane dianhydride, double (2,3-ic ^ ¢(2,3-,3⁄4 3, 4-^^^ base > wind 2 11' b double (2' 3_ or 3, 4_ two solution base) _ E-burn two Xuan and so on.

As other acid anhydrides, for example, 仏 or 1' 2, 9, 10-phenanthrene-tetracarboxylic dianhydride, 2, 3, 6, diterpene tetracarboxylic dianhydride, & 2 - double ( 3,4-Lai-phenyl) tetrafluoropropanone two-needle, 2,3,5,6-cyclohexane dianhydride, 2'3'6'7-naphthalenetetracarboxylic dianhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride T 1 '4'5,8-naphthalenetetracarboxylic dianhydride, 48__dimethyl_12,3,5,6,7-hexahydronaphthalene-1,2, 5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-κ 5, 8_tetradecanoic acid, 2' 3' 6' 7- (or I 4, 5, 8 -) tetrachloronaphthalene-1,4,5, 8-(or 2, 3, 6, 7-) tetra-retensive dianhydride, 2,3,8,9-,3,4,9,10-,4 , 5,1〇,1b or 5,6,11,12-茈-tetracarboxylic dianhydride, cyclopentane_1,2,3,4_tetracarboxylic acid diacetic anhydride, pyridin-2,3 , 5,6-tetracarboxylic dianhydride, pyrrolidine 2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4'5-tetracarboxylic dianhydride, 4,4,_double (2,3-Carboxyoxyphenoxy)diphenylmethane dianhydride. As the diamine used for forming the low thermal expansion polyimine resin, preferred examples are: 4,4'-diamine diphenyl ether, 2'-methoxy group 4,4,-diaminophenyl hydrazine Stupid amine, 1,4-bis(4-aminophenoxy)benzene, 13-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy) Benzene]propane, 2,2,-diindolyl-4,4,-diamino-based stupid, 3,3'-dihydroxy-4,4,-diaminobiphenyl, 098104040 18 200945980 4'4 '-Diaminobenzidine aniline or the like as a diamine, preferably exemplified by: 2' \bis[4-(3_amine-siloxy)), bis[4_(4-aminophenoxybenzene) Grinding, bis[4-(3-aminophenoxy) stupyl] hard, bis[4_(4-amino group)] stupid, double [4-(3_amine county)] Bismuth, biguanide-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenyloxy) stupid Methane, bis[4-(3-aminophenoxy)phenyl]methane, bis-[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-amino) Phenoxy)phenyl]indole, bis[4-(4-aminophenoxy)]diphenyl, bis[4-(3-aminophenoxy)]diphenyl ketone, bis[4, 4,-(4-amine Phenoxy)]phenylaniline, bis[4,4-(3-aminophenoxy)]phenylanilide, 9,9-bis[4-(4-aminophenyloxy)phenyl]g 9,9-bis[4-(3-aminophenoxy)phenyl]anthracene, etc. As other diamines, for example, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4'4'-methylenebis-indole-toluidine, 4, 4 '-Methylene-2,6-dimethylaniline, 4,4'-methylene-2,6-diethylaniline, 4,4,-diaminodiphenylpropane, 3,3' _Diaminodiphenylpropane, 4, 4,-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4,-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Hard, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl Ether, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimercapto-4,4'-diaminobiphenyl, 3,3'-dimethoxyoxybenzidine, 4 , 4"- 0981 04040 19 200945980

:Amino-p-terphenyl, 3,3"-diamino-p-terphenyl, m-phenylenediamine, p-phenylamine, 2,6-diamine pyridine, 1,4 bis (4 _Aminophenoxy) stupid, n bis(4-aminophenoxy) stupid, 4 4,~[14_phenylphenylbis(diphenylethylene)diphenylamine, 4, 4'-[1 , 3-butyl bis(polyethylidene)] bis-amine, bis(P-aminocyclohexyl) fluorene, bis(pi-amino-dodecylphenyl), bis (P_f methyl one) Aminopentyl)benzene, P-bis(2-methyl-4-aminoindenyl)benzene, P-bis(1,b dimethyl-5-aminopentyl)benzene, (diamine) Kecai, 2'6-monoaminonaphthalene, 2,4-bis(no-amino-t-butyl)toluene, 2,4-^-toluene, m-xylene-2, 5-diamine, P-xylene-2,5-diamine: m- Benz P-monoamine, 2,6-diamino hydrazine, 2,5-diaminopyridinium, 2'-5-diamine Base ~1,3, 4-» and other diazoles, piperage and so on.

The acid needle and the diamine may be used alone or in combination of two or more. Further, it is also possible to use, together with the above-mentioned acid or diamine, the use ratio of the other acid or amine which is not contained in the above formula (7) octa-anhydride or -amine 'in this case' not included in the above formula (7) is preferably (10) The molar percentage is below, and the molar percentage is preferably ^. Control of thermal swell, adhesion, glass transition point (Tg) by selecting the surface of the acid needle or diamine, or by using two or more types of: wild or amine, and selecting the respective molar ratios. Wait. A precursor solution of a non-thermoplastic polyimine resin, which is also commercially available, can be suitably used. For example, a non-thermoplastic polyimine made from Ube Industries, Ltd.: a resin varnish (-) (4) Plus (trade name), same as kVarnish_s (trade name). 098104040 20 200945980 [Step b: photoresist pattern forming step] Then, as shown in FIG. 1 and FIG. 2(b), the surface of the coating film 3a formed as described above is coated with the photoresist layer 5 as a mask to form light. Resistance pattern (step S2). A well-known method can be used for formation of a photoresist pattern, and it is not specifically limited. For example, a photosensitive photoresist can be laminated or applied on the surface of the coating film 3a to form a photoresist layer 5, followed by exposure, development, and hardening to form a photo-pattern technique of a photoresist pattern. ❹ [Step c: Metal deposition layer forming step] Next, in the method of manufacturing the circuit board of the present embodiment, as shown in FIG. 2 and FIG. 2(c), in the exposed region which is not blocked by the photoresist layer 5, Is the metal deposition layer formed by reducing the metal in the coating film 3a? (Step μ). The material of the reduction treatment is (4) type diligence and legal wealth. The wet reduction method is a method of reducing metal ions in an exposed region which is not blocked by the photoresist layer 5 by dipping the coating film 3a into a solution (reducing agent solution) containing a reducing agent. In the wet reduction method, it is possible to suppress the metal ions existing inside the coating film (for example, the deep portion of the remaining portion or the coating portion directly under the light _ 5) from being reduced at the place where it is located. It is an effective method to preferentially precipitate the metal in the surface layer portion of the coating film 3a while riding in a metal shape. Further, in the wet reduction method, unevenness in metal precipitation is less, and a uniform metal deposition layer 7 can be formed in a short time. The metal deposition layer 7 thus obtained is partially embedded in the surface layer portion of the coating film 3a (polyimine precursor resin layer), so that high adhesion can be obtained. 098104040 21 200945980 As a reducing agent, a compound such as a amide compound such as a base amine warfare can be used as a gas in a sub-solution, for example, a compound of borax, hydrogenated potassium, sodium dimethate, formate, and hydrazine. The compound of the compound is used for the production of the original agent. Within the range of the reducing agent, it is preferable that the concentration of the compound is __, for example, 005~〇.5 molar solution. If the reduction is as low as possible, the reduction of the metal ions in the coating film a will be insufficient. Due to the action of the suture, the pre-formal material of the pre-mineral material will dissolve into the 10-type reduction treatment and will not be light. The area covered by the resist layer 5 is impregnated with SI. ,. Within the range (to 50~7 = agent money in 2. seconds ~ 3 ❹ minutes (to 3. (four) minutes two knives ~ 5 minutes for better) 昧 η. genus from early morning n s1 fine by dipping, The gold in the coating film 3a is reduced by the action of the original agent, and the metal is precipitated into a particle shape on the surface of the coating film. The end point of the reduction is outside the surface layer portion of the coating film 3a (for example, deep layer). The state in which the metal layer is almost absent immediately below the portion or the secret layer 5. The reason is that the metal concentration in the coating film % of the coating film 3a is uniformly distributed under the concentration distribution of the metal ions in the coating film. - The surface layer of the unmasked area in the coating crucible 3a moves, and the moving metal ions are reduced in the vicinity of the surface layer to precipitate a metal. At the end point of the reduction, there is almost an ion remaining in the coating 貘3a towel. In the form L#, metal ions remain in the coating film 3a, and residual metal ions can be removed by acid treatment described later. The determination of the reduction end point 098104040 22 200945980 疋 For example, the cross section of the coating film 3a can be used. Determination of 'read residual gold' by energy dispersive X-ray (EDX) knife analyzer In the present embodiment, the metal deposition layer 7 which is the seed layer of the circuit wiring 9 is only a portion which is covered with the photoresist layer 5 which is not formed in the pattern, and is in the light P layer. The lower part of 5. The 卩 is not formed. The result does not need to be used to remove the quick layer of the 'speed 剌 (1) sleeve etdllng) step, which can reduce the number of steps and improve the reliability of the circuit 布线 wiring substrate. [Step d: circuit wiring forming step Next, as shown in FIG. 1 and FIG. 2 (4), a patterned circuit wiring 9 is formed on the metal deposition layer 7 by electroless plating and/or plating (step S4). The electroless recording system is formed by The coating film of the metal deposition layer 7 is applied to the electroless ore solution in a secondary crushing process (electroless plating step), whereby the electroless plating layer can be formed by the electroless mineral deposit. The core of the plating after the enthalpy. ϋ As the non-electrolytic ore solution used in the electroless plating step, the influence of the difficulty on the precursor of the brewing imine is considered to select the neutral to weakly acidic hypophosphorous acid system. It is better to record the plating solution or (4) the plating solution. The phosphite-based nickel plating solution of commercially available products include, for example: TQP_Nik_d ^; Wei Qian Okuno Industry (shares) Ltd.). In addition, as a commercial item of the ship's liquid of (10), for example, Tc)p~Chemiall〇y B-1 (trade name; manufactured by Okuno Pharmaceutical Co., Ltd.) 'Top~Chemiaiioy 66 (trade name; Okuno) Pharmaceutical Industry (shares) 098104040 23 200945980). Further, the pH of the electroless plating is preferably adjusted to a neutral to weak acidity of 4 to 7. In this case, for example, an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, boric acid or carbonic acid, an organic acid such as acetic acid, glycolic acid, citric acid or tartaric acid may be used, or boric acid, carbonic acid, acetic acid, citric acid or the like may be combined. The weak acid and its alkali salt provide a buffering effect. The temperature of the electroless plating is preferably in the range of 80 to 95 ° C, more preferably in the range of 85 to 90 ° C. Further, the treatment time of the electroless plating step may be set to 20 seconds to 10 minutes, preferably 30 seconds to 5 minutes, and more preferably 1 minute to 3 minutes. Then, electroplating is performed by electroless plating using the electroless plating layer as a core (electroplating step). The plating layer is formed by electroplating to cover the electroless plating layer. Electroplating is carried out in a plating solution containing a composition of, for example, sulfuric acid, copper sulfate, hydrochloric acid, and a glossing agent (for example, Machusbeck (trade name) manufactured by Mademan Co., Ltd., which is a commercial product). The plating layer is used as a cathode, and a metal such as Cu is used as an anode. The range of the current density in the electroplating is preferably in the range of, for example, 0.2 to 3. 5 A/dm 2 . Further, as the anode of the electric ore, for example, a metal such as Ni or Co other than Cu can be used. After the circuit wiring 9 having the pattern is formed, the unnecessary photoresist layer 5 is peeled off, and the method of peeling off the photoresist layer 5 is not limited, and for example, it is preferably impregnated with a sodium hydroxide aqueous solution having a concentration of 1 to 4% by weight. A method in an alkali solution such as an aqueous solution of cesium hydroxide. In addition, when the photoresist layer 5 is removed after the imidization, the action of the alkali solution for the photoresist stripping or the like may adversely affect the deterioration of the polyimide resin, and the photoresist layer 5 Stripping is preferably carried out in the next step of the polymerization of the yttrium of the 098104040 24 200945980 fe fe fe 刖 刖 。 。 。. However, in the case where the photoresist layer 5 is formed as a part of the inter-circuit insulating layer of the circuit wiring 9, the peeling of the photoresist layer 5 is not necessary and is not limited thereto. Here, the removal of the metal ions in the coating film 3a will be described. In the wet reduction treatment, for example, in the case of using a metal salt such as phosgen hydroxide, lanthanum hydroxide or dimethylamine boron, or in the peeling of the photoresist layer 5, hydrogen is used. In the case of a metal salt such as potassium, there is a case where a metal ion derived from the metal salt is present in the coating film 3a, so that it is preferably removed. The removal of metal ions can be carried out by immersing in an aqueous acid solution. In this case, the applicable acid 'dissociation of metal ions for coordination with the carboxyl group of poly-proline to select a stronger acid than polyamine (The acid dissociation constant pKa is 3.5 or less) is preferably 'further' to select an acid which does not dissolve the metal precipitated by the reduction. Specific examples of such an acid include citric acid (pKa-2.87) and oxalic acid (pKa=1. 〇4). Further, hydrochloric acid, nitric acid, sulfuric acid or the like has a strong acid which dissolves the metal precipitate layer 7, and acetic acid (pKa = 4 56) has a low acid strength and is difficult to give away metal ions, which is not preferable. As a condition for removing the metal ions, it is preferable that the concentration is in the range of the weight % of the dip (preferably in the range of 5 to 1% by weight), and the temperature is 20 to 50 ° C. In the aqueous solution of the acid in the range, it is immersed in the range of 2 to 1 minute. The metal ions from the metal compound remaining in the coating film 3a can also be simultaneously removed by performing the reduction of the t-acid 1 after the end of the reduction or after the photoresist layer is peeled off. Further, the removal of metal ions is disclosed, for example, in "The 17th Microelectronics Discussion 098104040 25 200945980 (Microelectronics Symposium) Proposal Collection", September 2007, pages 179 to 182. [Step e: hydrazine imidization step] Next, as shown in FIG. 1 and FIG. 2(e), the coating film 3a is imidized by heat treatment to form the polyimide film layer 3 (step S5). ). The method of ruthenium imidization is not particularly limited. Preferably, for example, it is possible to heat at a temperature in the range of from 1 to 60 minutes under a temperature range of from 80 to 400 °C. In order to suppress the metal ◎ oxidation of the circuit wiring layer 9 formed by reduction and plating, it is preferable to heat-treat in a low-oxygen environment, specifically, in an inert gas atmosphere such as nitrogen or a rare gas, hydrogen, or the like. It is preferred to carry out the reducing gas atmosphere or in a vacuum. Further, the imidization step in the step S5 is preferably carried out after the circuit wiring forming step of the step S4, but it is also carried out before the step of the step s4. [Step f: Metal ion impregnation step] In the method for producing a circuit wiring board of the present invention, it is preferable that after the step a, the coating film 3a is further provided with an aqueous solution containing a metal ion. The metal ion solution is impregnated and dried to thereby increase the content of metal ions in the coating film 3a. By this impregnation, the free radicals present in the coating film 3a (i.e., the base which does not form a salt with the metal derived from the metal compound) become a metal salt. The metal ion used in this step f (metal ion impregnation step) can be the same as the metal compound of 098104040 26 200945980 contained in the coating liquid used in the above step a (coating film forming step). In the metal ion solution used in the metal ion impregnation step, a pattern containing a metal compound of 30 to 300 mM is preferably a cluster, and more preferably a range of 50 to 1 _. If the metal compound is 4 or less than 30 mM, the time required for the metal ions to be impregnated into the coating film may be too long, so that it is not preferable, and if it exceeds the surface of the coating film 3a, there is a residue ( Dissolve). ❹ A metal ion solution, such as a buffer for metallization of Mm pH. The impregnation method is not particularly limited as long as it can contact the metal ion solution with the coating, and can be used by a known/surface method, for example, (4), spray, and brush coating: the degree can be 0. ~1〇〇°C, preferably at room temperature near 20~ machine. The temperature of ^ is used in the case of using the dipping method, for example, in addition, the impregnation of the sickle bird 5 f D+, ❹ is preferably 5 minutes to 2 hours. The impregnation time is excellent even if it is superv, and the impregnation degree of the metal ion to the coating film 3a is constant to hour, and it is required to be dried after impregnation. The drying method is not particularly limited, and tends to be. However, it is dry, blown dry with air, or baked with a dry dream such as π iron, preferably 10 to 15 minutes under 10 to 15 minutes, ‘, etc. Dry strip ^ 25 ~ 1c π 〇 seconds ~ 30 minutes is better, to 30 ~ greasy down ^ min 〇 0 down 1 〇 After step ί, step b light m pattern shape, horse more 隹. The metal precipitation layer forms a step, but the amount of the metal can be 098104040 27 due to the coating film of the amine precursor resin layer having the steps of step = step and step c (ie, 200945980 film 3a) The content of metal ions is increased). As a result, since the metal deposition layer 7 obtained by the step is formed into a film shape, the electroless plating step can be omitted. In the electroless plating, there is a problem that the management of the plating solution and the disposal of the waste liquid are complicated. Therefore, if the electroless plating can be used, the circuit wiring excellent in adhesion to the substrate can be formed, and the industrial value thereof can be obtained. Very big. Based on such considerations, it is particularly preferable to form the coating film 3a in the step a, and then perform the metal ion impregnation step of the step f to increase the amount of metal ions in the coating film 3a. Moreover, depending on the material of the photoresist used in the step of forming the photoresist pattern in step b, the photoresist layer 5 not formed with the pattern may be coated after step b (ie, before step c). The exposed portion of the film 3a is brought into contact with the metal ion solution to carry out the metal ion impregnation step of the step f. [Step g: Amine Treatment Step] Further, in the method for producing a circuit wiring board of the present invention, it is preferable that the step a) is further provided with: g) ammonia or a first amine to the coating film % or A step of impregnation of a 2-grade aqueous amine solution. By impregnation with an aqueous solution of ammonia or a 1:min or a second aqueous amine (hereinafter also referred to as an aqueous amine solution), the amine in the aqueous amine solution will chelate with the metal ions present in the coating film 3a. The ligand is substituted with a ligand to form an amine complex of metal ions. When the metal ion is reduced, the ligand becomes a state in which it is easily liberated, and as a result, the metal ruthenium ion can be uniformly formed in the surface layer portion of the coating film 3a. Grade 1 thief 2 grade H is water soluble (four) Yes, no - special, but aliphatic amines are preferred. Specific examples of such aliphatic amines 098104040 28 200945980 200945980 Alcoholamines, butanolamines, and diethylamines are exemplified by ethanolamine, dipropanolamine, ethylenediamine, diethylamine and the like. Further, among the bis, diethanolamine, monopropanolamine, butanolamine, diethanolamine, and dipropylamine aliphatic amines, it is more preferable to use an alcoholamine such as ethanolamine or the like, which is easy to use and economical. good. Preferably, the solution is preferably present at a concentration of from 1 to 3 Torr. It is preferably in the range of the weight % of the amine water, and the liquid temperature is within the range of 1 〇 to 30. (It is preferably in the range of (::)). The range of the amine is water-soluble (with 10 to 50 ❹). For example, the three-time method of the dipping method and the spraying method can be used, and the dipping method is not particularly limited, and the sewing material is processed for 10 seconds to 2 seconds. For example, 'in 2 hours (1 to 30 minutes is preferred) If the concentration or temperature of the aqueous amine solution does not reach the above lower limit, there is a tendency that the ligand substitution is incomplete, and if the upper limit is exceeded, the metal ions in the coating film 3a may be easily eluted. The coating film 3a after impregnation can be directly delivered to the next step, and the coating film 3a can be dried after impregnation. 之后 After the amine treatment step in step g, the photoresist of step b can also be performed. In the pattern forming step and the metal deposition layer forming step in the step c, the metal deposition layer 7 obtained in the step c is formed into a film shape by the step g, so that the electroless plating step can be omitted. Step g and omitting the case of the electroless plating step The thickness of the coating film 3a is preferably 2/zm or more. By making this thickness, a sufficient amount of metal ions can be contained in the coating film 3a. Further, the metal ion impregnation step of step f and the step g are The amine treatment step can be carried out only by performing 098104040 29 200945980. In this case, it is preferable to form a dense film-like metal deposition layer 7'. In the case of performing both step f and step Regardless of the order, it is preferable to carry out the step g after the step f. ——*, the green of the electric-ray substrate of the present embodiment is green, and by performing the above steps a to e', step f can be performed if necessary. And/or a step circuit, a circuit wiring board in which the circuit wiring 9 having excellent adhesion is formed on the insulating material layer having the polyimide 1 and the polyimide resin layer 3 can be formed. There is no need for special (four) materials and U (four) methods, and there is no need to use the steps to remove the metal deposition layer, so the industrial use value is very large. Secondly, the present invention is specifically illustrated by the examples, The invention is not so etc. The embodiment is not limited in any way. Further, as long as there is no special purpose, the various measurements and evaluations are based on the following. Further, the abbreviations used in the present embodiment are the same as above. [Evaluation of adhesion In the evaluation of the nature of the bird's eye, a test piece for measuring the circuit wiring of 3 inches wide was produced, and it was evaluated by Strograph Ml (manufactured by Toyo Seiki Seisakusho Co., Ltd.) by measuring the strength in the direction of 90 in the direction of the dish. As for the evaluation of the adhesion, as long as the tensile strength is 〇.5 kN/m or more, there is no problem in practical use, but in order to obtain more excellent adhesion, it is preferably 1.0 kN/m or more. [Line thermal expansion coefficient The measurement of the linear thermal expansion coefficient was carried out by using a Thermo-Mechanical Analyzer (manufactured by Seiko Instruments Co., Ltd.) to raise the temperature of the sample to 25 ° C, and then maintaining the temperature for 1 minute. The cold section at a speed of 5 〇 c/min was evaluated by finding the average linear thermal expansion coefficient (CTE) from 24 loo to loot. [Measurement of glass transition temperature] Glass transition temperature 'Use viscoelastic analyzer (Rheometric

Science F_ Ε·() rsA-II) 'With a sample of l〇mm width, while applying a vibration of 1 Hz to the side while raising the temperature from room temperature to 400 c at a rate of 10 ° C / min 'It is obtained from the maximum value of the loss tangent (Tan5). [Measurement of the average particle diameter of the metal particles precipitated after the reduction treatment] The cross section of the sample was observed by a scanning electron microscope (manufactured by Hitachi Hitechnologies Co., Ltd.) at a magnification of 5 〇, and the average of the whole metal particles was observed. Particle size. [Measurement of sheet resistance of metal layer] G The sheet resistance of the metal layer was measured by a method according to JIS K 7194 using a resistance measuring instrument (MCP-T610 manufactured by Mitsubishi Chemical Corporation). In addition, when the measured value of the sheet resistance of the metal layer is more than 50 Q / 〇 (〇hm / square), the level of "hard plating" is evaluated, and when it is 50 Ω / □ or less, the level of "electroplating" is evaluated. In addition, when it is 30 Ω / □ or less, it is evaluated as a metal layer, and it is "excellent" as a conductive film. [Evaluation method of anti-warping] The conductor layer was formed into a resin film by a cutting machine to prepare a test piece of 1 Ocm x 10 cm 098104040 31 200945980 size, and the test piece was placed on the table and the highest part of the table was arched from the table top. The twist is measured with a vernier scale (nonius). The amount of the anti-warpage of the resin film formed by using this height as the conductor layer was evaluated as "no ruthenium" when the amount of anti-warpage was less than 2 mm. [Production Example 1] In a 500 ml separable flask, 2 _. 7 g of 2,_. 曱oxy-4,4,-diaminophenyl anilide (0·08 mol) was stirred with stirring. Dissolved in 343 g of DMAc. Then, 28.5 g of PMDA (〇·13 mol) and 10.3 g of DAPE 44 (0.15 mol) were added to the solution under a nitrogen stream. Then, the I-coupling reaction was carried out while stirring was continued for about 3 J to obtain a viscous polyimine precursor resin solution Si. The obtained polyacrylimide precursor resin solution Si was coated on a non-recorded steel substrate, dried at 130 C for 5 minutes, and heated to 36 generations in 15 minutes to complete the yttrium imidization to obtain a laminate on the non-fine substrate. (4) an imine film. The polyamidide film was peeled off from a stainless steel substrate to obtain a 25 mm thick polyimine 0 film S2. The linear thermal expansion coefficient of the polyimine film &amp was 14·6 χ 1 (Γ6 (1/Κ). [Production Example 2] In a 500 ml separable flask, the crucible was stirred under stirring (0. 05). The molars were dissolved in 25 μg of DMc, and then 14.7 g of BPDA (〇.〇5 mol) was added to the solution in a gas stream. Then, the polymerization was carried out while continuing to stir for about 3 j. Adhesive polyacrylimide precursor tree 098104040 32 200945980, · Lipid solution τ!. The obtained polyamidene precursor resin solution T1 was coated on a stainless steel substrate and dried at 130 ° C for 5 minutes. The temperature of the coating was raised to 36 〇/C in 15 minutes to complete the imidization of the coating film, and the substrate was removed to obtain a film thickness of polyimine film. The glass transition temperature of the obtained polyimide film I was 252°. C, the coefficient of thermal expansion of the wire was 52 χ 1 (Γ6 (1/Κ). [Production Example 3] 7 7·91 g of pyridine was added to the polyimine precursor resin solution prepared in Production Example 2 (〇.丨莫[ear]) Stir for 20 minutes. Add this commercially available nickel(II) acetamidine acetate dihydrate 22·0g (0·08 mol) to 160ml. A solution of N-mercapto-2-pyrrolidone (hereinafter abbreviated as NMp) was stirred at room temperature for 1 hour to prepare a blue polyimine precursor nickel complex solution A. Production Example 4] G A test piece of an alkali-free glass (AN-1 制 manufactured by Asahi Glass Co., Ltd.) was treated with 12.5 cm x 12.5 cm (thickness: 0.77 mm), and treated with a 5N aqueous sodium hydroxide solution at 50 ° C for 5 minutes. Then, the glass substrate of the test piece was washed with pure water, and after drying, it was immersed in a 1% by weight aqueous solution of 3-aminopropyltrioxoxacin (hereinafter abbreviated as "γ-APS"). After the glass substrate was taken out from the r-APS aqueous solution, it was dried while being heated at 150 C for 5 minutes to obtain a glass substrate. [Example 1] The thickness of the glass substrate G was imidized to 丨·4 μιη The square 098104040 33 200945980 coated polyimine precursor nickel complex solution A was dried at 13 ° C for 20 minutes to obtain a coating film ai. Then 'dry film resist on the surface of the above coating film a Agent (Asahi Kasei (stock) system 'product name: Sunphoto AQ, l〇 / zm thickness) is laminated at a temperature of ii 〇 ° c, through the mask External exposure 'developed with 0.5% by weight aqueous sodium carbonate solution' to form a photoresist pattern of 50//m {wiring width/wiring interval (L/S)=20//m/30//m} The glass substrate bl of the photoresist pattern. The glass substrate bl is immersed in a 50 mM sodium borohydride aqueous solution (5 〇 ° C) for 3 minutes to form a nickel deposition layer on the surface of the coating film ai which is not blocked by the photoresist layer. , the glass substrate cl is obtained. As a result of observing the cross-section of the surface layer portion of the coating film a, it was confirmed that the nickel particles (nickel) having an average particle diameter of about 4 Å were present from the outermost surface of the coating film a1 to a bed of about 1 〇〇ηη. The particles are in a buried state). Then, the glass substrate cl was immersed in an electroless nickel ore bath (manufactured by Okuno Pharmaceutical Co., Ltd., trade name: TQp_Nik〇r〇n-Li-S) for 30 seconds. A recording layer of a substrate as a copper bond. Further, the formed nickel layer was subjected to electro-mineralization at a current density of 2 A/dm 2 at the current of copper plating to form a copper wiring of copper sputum in, wind and degree 1, and a glass substrate cH was obtained. The obtained glass substrate dl was immersed in a 2% by weight aqueous sodium hydroxide solution (25C) for 3 minutes. The photoresist pattern was peeled off and then immersed in a 1% by weight aqueous solution of oxalic acid (scratch). This removes the former metal ions. After the glass substrate dl was washed with ion-exchanged water, it was heated to a maximum of 098104040 200945980 under a nitrogen atmosphere, and the ruthenium imine precursor was imidized at the same temperature for 5 minutes. The woven fabric was cooled to a normal temperature in a nitrogen atmosphere, and a glass substrate el, which was formed with a copper wiring, was formed, and the copper wiring was pulled at a strength of 14 kN/m, and the adhesion was excellent. [Example 2] 、 On a stainless steel substrate, the thickness of the yttrium iodide was made into a square = cloth-polyimide precursor resin solution Si, which was dried by 2 〇W at 13 °c [ The imine precursor resin layer was obtained. The polyimine precursor precursor was recorded on the resin layer in such a manner that the thickness of the powder was changed to L4 " m. Body solution A, obtained by working on the dry (four) minutes. In the same manner as in the example i, except that the coating film a1 in the example i was changed to a coating film, the polyimide layer b2 in which the photoresist pattern was formed and the precursor resin layer c2 were formed were formed. The copper cloth & 2 drive resin layer is made up of the copper-lined polyimide resin. The result of cross-section observation of the surface layer of the coating film a2 is confirmed. The surface is about 100 nm deep—the particles (the silk particles are in a state of being embedded), and the poly-imine resin layer e2 is peeled off from the steel substrate by 2mr^_e2'. The shaft has copper wiring. The tensile strength of the steel wiring is dense [Example 3] 098104040 35 200945980 Using the coating of nickel acetate solution in Example 2 (25. In the crucible, the coating film & 2 was immersed in the lion n L θ 10 minutes The nickel ion is impregnated into the coating film a2 to form the metal ion-containing layer (5). In addition to the use of the metal ion complex, the film i-imine precursor resin layer b3 and the method of the fourth embodiment are replaced with the example (i) A poly-baked (four) «layer eh precipitation precursor resin layer C3 formed with a photoresist pattern is obtained. The sheet resistance of the electrode layer which is particularly excellent before the precipitation of nickel is _□, and is used as a pre-extrusion of 2 Α~ The resin layer C3 is subjected to electro-recording in copper electrical wiring to form a copper film thickness of 1 〇 _ with a steel wiring before the resin layer d3, and e3 is obtained by the method of the embodiment 1 (10). The (IV) imide resin layer of the copper wiring is not peeled off from the steel substrate, and the (4) imine resin layer e3 of the Z-made steel wiring is formed from the copper wiring. The degree of the obtained is + (4) , the tension of the _ line is strong [Example 4] 'The thickness of the coating on the uncoated steel base For the m-like side, the poly-brew = _ resin solution - dried in the C for 20 minutes, the thickness of the layer is turned into a $ 2 ^ layer. In this resin layer, the ship imine solution a, in the Wei frequency Record the wrong cloth film a4 immersed in 25 weight = (four) 'get it... apply this 氦 aqueous solution (25. 〇 2 minutes, make it contain 098104040 〇〇36 200945980 / again to the coating film a4. Then 'will The coating film a4 was pulled up from the aqueous ammonia solution and dried to obtain a coating film a4. The same procedure as in Example 1 was carried out except that the coating film & 4' was used instead of the coating film U in Example i. A polystyrene layer formed with a photoresist pattern::=Γ? layer b4 and a precursor resin layer c4 are deposited. The sheet resistance of the precipitated layer in the nickel precipitation precursor $曰θ c4 is 42 Ω/α ❹ film. Nickel precipitates the precursor resin layer c4, in the electrolysis of copper electricity 2A/dm2, the electroplating is cold, and the copper ore is formed into a copper film with a thickness of 1〇__ The resin layer d4 was obtained by the polyimine resin layer e4 in which the copper wiring was formed in the same manner as in the example i 5. The polyimine resin layer 64 formed with the steel wiring was not recorded from the steel-based wiring. Γ (4) is formed into a copper wiring film e4'. The copper iridium 1: e4' is formed, and the copper wiring has a tensile strength of 1.4 kN/m, and the adhesion is excellent. n [Example 5] 225 In addition, the remainder = (10) water frequency 2 (four) impregnation for 2 minutes, the sheet of the precipitated layer of the yttrium imide precursor tree c5, the resin layer c5 is deposited, and the resin layer is deposited. The film was plated to form a steel film thickness, and the current density of 2 A/dm 2 was used to enter the copper wiring of the shell, and the copper wiring 098104040 200945980 was formed without the precursor resin layer d5' being the same as in the first embodiment. This results in a polyimine resin layer e5 formed with a copper wiring. The obtained polyimide film layer e5 on which the copper wiring was formed was peeled off from the stainless steel substrate to obtain a film e5' on which the surface wiring was formed. The film e5 having the copper wiring formed thereon was obtained, and the copper wiring had a tensile strength of 1.4 kN/m, which was excellent in adhesion. [Reference Example] A polyimide film (manufactured by Toray-DuPont Co., Ltd., trade name: Kaptc > nEN, 100 mm x 100 mm x 25 / zm thick, linear thermal expansion coefficient (CTE) 16 x 1 (T6 / K) was immersed at 50 ° C 5N potassium hydroxide aqueous solution was used for 1 minute. Then, the impregnated polyimine film was sufficiently washed with ion-exchanged water, and then immersed in an aqueous solution of hydrochloric acid (25 ° C) for 30 seconds. Then, it is sufficiently washed with ion-exchanged water and spray-dried with compressed air to obtain a surface-treated polyimine film. The thickness of the alkali-treated layer on one surface of the surface-treated polyimine film is 1.4 μm. The film was immersed in a 100 mM aqueous solution of nickel acetate (25 ° C) for 10 minutes, and a metal ion-containing layer was formed by impregnating the treated layer with nickel ions. Then, a dry film photoresist was formed on the surface of the metal ion-containing layer (Asahi Kasei (share), Shangyi name. Sunphoto AQ, l〇em thickness) is laminated at a temperature of ii 〇 °c, exposed to ultraviolet light through a light mask, and developed by a 5 wt% aqueous solution of sodium carbonate. # m{Wiring width/wiring interval (L/S)=20 in m/30 a resist pattern of //m}, and a film formed with a photoresist pattern is obtained. The above-mentioned thin crucible is immersed in a 50 mM aqueous solution of sodium borohydride (5 〇. 3 minutes 098104040 200945980 〇 in the masked area without the photoresist layer) On the surface of the metal ion-containing layer, a precipitated layer is formed to be immersed at a temperature of 8 〇. (: an electroless nickel plating bath (manufactured by Okuno Pharmaceutical Co., Ltd., trade name: Top-Nikoron T0M-S) 30 seconds, borrowed •• This is formed as the riding layer of the steel lai. Then, in the formed nickel layer, in the copper plating bath, the copper wiring of the plating-degree W is carried out with a current density of 2A/W. For the formed steel wiring, _=copper=, the pull-off strength is 0.7 kN/m. Into the sweat evaluation, the above Examples 1 to 5 and the reference γ are shown in Table 1 and Table 2. Summary of the test and test results

098104040 39 200945980 [Table 1] Example 1 Example 2 Example 3 Coating film (polyimine precursor resin layer) Type of single-layer, 2-layer, 2-layer metal ion impregnated polyimide resin Thermoplasticity (Tg= 252〇C) Thermoplasticity (Tg=252〇C) + Low thermal expansion [CTE=14.6 xlO'6(l/K)] Thermoplasticity (Tg=252〇C) + Low thermal expansion [CTE=14.6 xlO_6(l /K)] In the state of the metal (Ni) precipitation layer, the Ni particles having an average particle diameter of 40 nm are in the buried state, and the Ni particles having an average particle diameter of 50 nm are in a buried state (sheet resistance: 25 Ω/Π). Do not pull the tensile strength [kN / m] 1.4 1. 4 1.4 [Table 2] Example 4 Example 5 Reference Example Tu Wei film (polyimine precursor resin layer) 2 layers of ammonia impregnation 2 layers of ethanolamine impregnation test Type of Polyimine Resin Treated Thermoplasticity (Tg=252〇C) + Low Thermal Expansion [CTE=14.6 xlO'6(l/K)] Thermoplasticity (Tg=252〇C) + Low Thermal Expansion [CTE= 14.6 xlO'6(l/K)] Low thermal expansion [CTE=16 xlO'6(l/K)] State of metal (Ni) precipitation layer Film (sheet resistance 42 Ω / Π) Membrane (sheet resistance 45 Ω / Π) — electroless plating In the procedure, the pull-out strength of the necessary wiring is not required [kN/m] 1.4 1.4 0. 7 098104040 40 200945980 It can be confirmed from Table 1 and Table 2 that the method of the embodiment 丨 to the embodiment 5 is manufactured as a circuit wiring substrate. The copper wiring forms a resin layer, and the tensile strength of either one is l./m' is very large. In the use of a flexible wiring board or the like: the required adhesion is far superior to the reference example. In particular, an embodiment of a surface resin layer in which the glass is converted to a thermoplastic polyimine resin (Tg=252 < 5c) ❹ ' of 35 GC or less by using the polyimine precursor nickel complex solution A In the case of the second embodiment, the nickel particles deposited in the metal deposition layer opening/forming step are present in a sufficient depth (about 1___||, which is embedded in the front layer of the thermoplastic polyimide resin. It contributes to the improvement of the adhesion. Further, the low thermal expansion polyimine resin in the range of the linear thermal expansion coefficient of $1χ1〇_6~grade ι〇_6(ι/κ) [GTE=14.6X1G, 1/ K)], the second layer of the above-mentioned thermoplastic poly-imine resin is laminated to form a multilayer structure. (4) Purely, the heat can be obtained by the same layer of the adjacent layer of the metallographic layer. The polyruthenium group, which is very excellent in nature and low in thermal expansion, suppresses the objectivity of the substrate. A laminated structure, thus showing that the coating film which can effectively ionize and accommodate the polyimide film of the polyimide precursor has a metal resistance of 25 [0/□], which is very small, so even if it is a rational Can directly ride the state of Wei treatment. The reason for this is that the metal ion is impregnated, and the amount of nickel ions in the coating film becomes rich in 098104040 200945980, so that the deposited metallic nickel layer can be formed into a dense film. Further, the coating film which is a resin layer of the polyfluorene-liner was subjected to a secondary decompression treatment in an aqueous amine solution, and in Examples 4 to 5 in which ammonia or amine was impregnated, the nickel precipitation layer after the reduction treatment was formed as In the form of a film, the sheet resistance is also small, up to 5 〇 [Ω / ΙΙ 1] or less, and it can be directly plated even if the electroless plating step is not performed. The reason is that the amine complex formed between the metal ion in the coating film by the impregnation of the aqueous amine solution has the property of allowing the ligand to be easily released when the metal ion is reduced, so the reduction of the metal ion It can be uniformly formed on the surface layer portion of the coating film, and the nickel deposition layer is formed into a film shape. The present invention is not limited to the embodiments described above, and various changes may be made without departing from the spirit and scope of the invention. (Industrial Applicability) The method of the present invention can be applied to the manufacture of a circuit wiring board such as a printed wiring board used in various electronic parts. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the main steps of a method of manufacturing a circuit wiring board according to an embodiment of the present invention. 2(a) to (e) are explanatory views of the respective steps of Fig. 1. [Main component symbol description] 1 Underlayer (substrate) 3a Coating film 3 Polyimide resin layer 098104040 42 200945980 5 Photoresist layer 7 Metal deposition layer 9 Circuit wiring 100 Circuit wiring substrate

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Claims (1)

200945980 VII. Application scope of δ 青青·· 1. A method for manufacturing a circuit wiring board, which is a circuit board substrate formed by forming a circuit wiring on a polyacrylamide resin layer; The step of escaping: a) forming a coating film by coating a coating liquid containing a poly-amine precursor resin (polyamide resin (4) and a metal compound on a substrate and drying it; b) a step of coating the surface of the coating film with a photoresist layer to form a pattern to form a photoresist mask; and) depositing a metal into the surface layer portion of the coating film by reducing metal ions in the coating film a step of forming a metal deposition layer without being covered by the photoresist mask; d) a step of forming a patterned circuit wiring by electroless plating and/or electric forging on the metal deposition layer; e) a step of forming the above-mentioned polyimine resin layer by heat-treating the polyimide phase of the polyimide film in the coating film. 2. The method of manufacturing a circuit board according to the first aspect of the present invention, further comprising: f) impregnating the coating film with an aqueous solution containing a metal ion, and drying the method; The step of increasing the content of metal ions in the coating film described above. 3. If you apply for a patent scope! The method for producing a circuit wiring board according to the invention, further comprising the step of: g) impregnating the coating film with an aqueous ammonia solution or an aqueous solution of a primary amine or a secondary amine. 098104040 44