TW200948891A - Resin composition for printed circuit board, dry film and printed circuit board - Google Patents

Abstract

The invention provides a resin composition for printed circuit concerning environment while maintaining enhancement characteristic of resin composition for printed circuit, a dry film and a printed circuit board using the same. The resin composition for printed circuit includes regenerated polyethylene glycol terephthalate.

Description

The invention relates to a resin composition for a printed circuit board which is excellent in insulation and heat resistance, and a dry film and a printed circuit board using the same in consideration of the environment [Prior Art] φ In recent years, the viewpoint of environmental issues, and printed circuit boards used in electronic equipment are also required to use materials that have an environmental impact. For example, due to the social problem of the generation of harmful gases such as dioxin during combustion, it is required to use a halogen-based material such as bromine or the like to a halogen-free material or a dye-dye material used for a prepreg or a solder resist film. The conversion. For example, the halogen-free material of the flame-retardant material of the composition for a printed circuit board has been subjected to various reviews (see, for example, Patent Document 1). However, the concern for environmental issues is raised and the environmental impact is further taken into account. On the other hand, since printed circuit boards are used in electronic equipment, they are required to have insulation properties. Further, in the interlayer resin insulating layer of a printed circuit board, since the electronic component is assembled at a high temperature, heat resistance is required. Further, in recent years, with the miniaturization of the pattern of the solder resist film formed on the outermost layer of the printed circuit board, the pattern formation is performed by the photolithography method. At this time, the activity is irradiated by the pattern of the transmissive mask. The energy line forms a pattern, and the resin composition for forming the solder resist film is required to have photocurability. In the case of the photosensitive resin composition, a halogen-free form having an environment of -5 to 200948891 has been proposed (for example, see Patent Document 2). As such, the resin composition for printed circuit boards is required to have both environmental impact and maintenance improvement characteristics. On the other hand, in recent years, PET bottles have been light, transparent, and gas-blocking, and the use of high-strength has increased rapidly. With this, the disposal method has gradually become a social problem. Therefore, various kinds of reviews have been carried out regarding the recycling of PET bottles (see Patent Documents 3 to 5, etc.). However, during the recycling process, the molecular weight of PET is reduced due to the hydrolysis of the ester bond, and the melt viscosity and mechanical strength of PET are reduced. Then, such a decrease in quality is a cause of obstacles to the recycling of PET bottles. Therefore, the state of the recycled PET resin is only used in the field of fibers or industrial materials. Along with the increase in the waste of PET bottles, the new and effective use of recycled PET resin is still being explored. [Patent Document 1] (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. 2000-7974 (A. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei No. 2000-53892 (Patent Document 5) Japanese Patent Application Publication No. 2000-53892 (Summary of the Invention, etc.) -6- 200948891 OBJECTS TO BE SOLVED BY THE INVENTION As described above, the resin composition for a printed circuit board is required to have environmental impact and maintenance improvement characteristics at the same time. Here, the present invention provides an environmental impact that can be considered at the same time. In addition, a resin composition for a printed circuit board and a printed circuit board using the same are used as the object of the invention. Φ [Means for Solving the Problem] In order to solve the above problems, a printed circuit board of one form of the present invention is provided. A resin composition containing regenerated polyethylene terephthalate (A). With such a structure, insulation, heat resistance, and light transmittance are excellent, and environmental effects are considered. Further, it is preferable to prepare a resin composition for a printed circuit board by using a regenerated polyethylene terephthalate fine powder having a mixed average particle diameter of 0.1 to 15 μm as a resin composition for a printed circuit board. The composition can simultaneously obtain good smoothness and insulation of the printed circuit board, and suppress pattern defects in pattern formation. Further, the resin composition for a printed circuit board, the regenerated polyethylene terephthalate (Α) is preferably 0.1 to 75% of the total amount. With such a configuration, it is possible to simultaneously obtain good fluidity, coatability, and formability of the resin composition for a printed circuit board, and to suppress the fragility of the cured product. Further, it is preferable that the resin composition for a printed circuit board contains a thermosetting resin (B) of 200948891. The thermosetting resin (B) can be cured by heating. A good permanent film is formed. The resin composition for a printed circuit board is preferably a photosensitive resin (C). By using a photosensitive resin (C), it can be irradiated with light. hardening The formation of a fine pattern by the photolithography method is possible. Then, the dry film of one embodiment of the present invention is characterized in that it is coated on the substrate with the above-mentioned resin composition for a printed circuit board. Dry film. With such a structure, a dry film excellent in insulation, heat resistance, and light transmittance can be obtained, and by transfer to a printed circuit board, a simple regenerated polyparaic acid B can be formed on a printed circuit board. The resin composition layer of the diester (A) is characterized in that the printed circuit board according to one aspect of the present invention is characterized in that the substrate is formed with a circuit, and at least a portion of the substrate is formed to enable the printing A permanent film which is cured by a resin composition for a circuit board. © With such a configuration, a printed circuit board excellent in insulation and heat resistance can be obtained. Further, a printed circuit board according to one aspect of the present invention is characterized in that: a substrate on which a circuit is formed, and at least a portion of the substrate is provided with a resin for a printed circuit board transferred by the dry film described above The composition is coated with a permanent film after the dried film is hardened. According to this configuration, a printed circuit board having excellent insulation properties and heat resistance and having an environmental impact can be obtained. -8 - 200948891 [Effects of the Invention] The resin composition for a printed circuit board of the present invention and the dry film or printed circuit board using the same can simultaneously take into consideration the influence on the environment and maintain the lifting property. [Embodiment] φ [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described. The resin composition for a printed wiring board of the present embodiment is characterized by containing regenerated polyethylene terephthalate (A). The regenerated polyethylene terephthalate (A) of the present embodiment is not particularly limited as long as it is a polyethylene terephthalate. For example, recycled PET bottles, etc., recycled, crushed, washed, recycled raw materials, or regenerated polyparaic acid obtained from PET bottles or PET films to defective products such as those produced in the manufacturing process. Ethylene glycol raw material. In the thus-regenerated polyethylene terephthalate raw material, it is preferred to use a polymer of ethylene phthalate alone or, depending on the case, a highly crystalline resin containing a small amount of a copolymer. In this case, the crystallinity can be made, for example, 35% or more by heat treatment. Further, a polyester resin, a denatured polyester resin or the like may be melt-mixed. Then, the thus-regenerated polyethylene terephthalate raw material is directly pulverized or slurried by mechanical pulverization or chemical pulverization, and then pulverized by using a jet mill or the like. The dispersion treatment or various classification devices are carried out to make the average particle diameter as 〇·1~15μιη used as 200948891. When the average particle diameter is less than 〇·1 μιη, the surface energy becomes high and it becomes easy to aggregate, and the smoothness and insulation of the printed circuit board cannot be sufficiently obtained due to the influence of the aggregate. On the other hand, if the average particle diameter exceeds 15 μm, the smoothness of the printed circuit board is impaired, and when the solder resist film is formed, defects due to defects of the pattern are caused. More preferably, the average particle size is 1 to 12 μm. Here, in order to prevent the above surface energy from becoming high, it is easy to aggregate, and it is also possible to operate in a slurry state in which the organic solvent is dispersed in advance. The average particle diameter at this time is not limited to the above, and it can also be used in a more subtle state. By repeating such fine pulverization, the PET is mixed with a thermosetting component, a photosensitive component, or the like to form a resin composition for a printed circuit board. In this case, the mixing ratio of the regenerated polyethylene terephthalate (A) is preferably from 0.1 to 75% by weight based on the total amount of the composition. If the environmental impact is taken into consideration, the mixing ratio is preferably more than 1% by weight. On the other hand, when it exceeds 60% by weight, the cured product of the insulating composition becomes brittle, and the fluidity of the insulating composition is lowered, which may cause problems in coating and molding. More preferably, it is 1 to 60% by weight. In addition to the regenerated poly(ethylene terephthalate (A), the resin composition for a printed wiring board of the present embodiment may contain various components such as a thermosetting component and a photosensitive component. As long as it is suitable for a printed circuit board, such as insulation, heat resistance, etc., it is not limited to a specific component, and it is preferable to select tm. Basically, various forms containing a thermosetting component or a photosensitive component or both components can be proposed. In general, when the thermosetting resin composition contains regenerated polyethylene terephthalate (A) and thermosetting-10-200948891 resin (B): a photocurable resin composition, it contains When the regenerated polyethylene terephthalate (A), the photosensitive resin (C), and the photopolymerization initiator (D) are used as a photo-curable thermosetting resin composition, the regenerated poly-pair is contained. Ethylene phthalate (A), thermosetting resin (B), photosensitive resin (C), photopolymerization initiator (D), and carboxyl group-containing resin (E). Then, the type of each of these components is appropriately selected, and by using a resin composition for a printed circuit board which optimizes the blending ratio, a cured product having desired properties can be obtained. The resin composition for a printed circuit board can be made to contain a thermosetting catalyst (F), a chelating agent (G), an organic solvent (H), or the like as needed. In the present embodiment, the thermosetting resin (B) is not particularly limited as long as it is excellent in the case where a cured product such as insulating properties is used for a printed circuit board, and specifically, a ring is specifically mentioned. Oxygen resin, phenol, urethane resin, polyester resin, hydroxyl group, amine group or carboxyl group-containing polyethyl urethane, polyester, polycarbonate, polyalcohol, phenoxy resin, acrylic Polymer resin, vinyl resin, polyimine, polyamidimide, oxazine resin, cyanate resin, oxycyclobutane compound, polyisocyanate, blocked isocyanate, carbodiimide (compound) resin, Oxazoline (compound) resin and the like. These may be used alone or in combination of two or more types. The blending ratio of the thermosetting resin (B) is from 10 to 100,000 parts by mass, more preferably from 30 to 100 parts by mass, per 100 parts by mass of the recycled PET powder (A). If it is less than 10 parts by mass, the fluidity is lowered. 'Coating or forming becomes difficult, and the mechanical strength is lowered. On the other hand, -11 - 200948891, if it exceeds 100,000 parts by mass, it is meaningless and unsatisfactory from the viewpoint of considering environmental impact. The photosensitive resin (C) is not particularly limited as long as it is a compound which undergoes radical polymerization by an ethylenic unsaturated double bond by irradiation with an active energy ray, and examples thereof include a (meth) acrylate compound and an unsaturated group. A polyester-based compound, an unsaturated urethane-based compound, a styrene-based compound, a butadiene-based compound, or the like. Among such ethylenically unsaturated compounds, a (meth) acrylate type compound is particularly preferable, and the (meth) acrylate type compound is monofunctional, polyfunctional, and monomeric, oligomer (pre Any one of the polymers may have a functional group other than an acryloyl group (methacryloyl group). Specific examples thereof include a substituted or unsubstituted aliphatic acrylate, an alicyclic acrylate, an aromatic acrylate, and a monomer such as an ethylene oxide-modified acrylate, or an epoxy acrylate or an amine. Oligomers such as ethyl acrylate, polyester acrylate, polyether acrylate, polyalcohol acrylate, alkyd acrylate, melamine acrylate, polyoxy acrylate, polybutadiene acrylate, and the like, and Corresponding to such methacrylates and the like. These may be used alone or in combination of two or more types. In order to increase the reactivity of the photosensitive resin (C), a photoreactive monomer may be added. Specific examples thereof include butoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, and hydroxyethyl (meth)acrylate. Hydroxypropyl acrylate, glycerol (meth) acrylate, 4-(methyl) aryloxytricyclo [ 5.2.1.02.6] decane, isodecyl (meth) acrylate, (methyl )C-12- 200948891 Isodecyl enoate, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) ) butyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 4-(methyl) aryloxy alkyl phosphate, r- (a Monofunctional (meth) acrylates such as aryloxyalkyltrialkoxydecane; acryloylmorpholine, N-vinylpyrrolidone, N,N-dimethylpropenamide, N-ethylene Monofunctional monomers such as carbazole, styrene, vinyl ethoxide, acrylonitrile, trialkoxyvinyl decane, etc.; bisphenol-A-di(meth)acrylic acid , alkylene oxide-denatured bisphenol-A-di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, 9. decanediol di(meth) acrylate, ethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(methyl)decyl acrylate, bis[4-(methyl)aryl Oxymethylmethyl]tricyclo[5.2.1.02.6]decane, bis[4-(methyl)aryloxy-2-hydroxypropoxyphenyl]propane, isophorone diisocyanate denatured urethane Ester di(meth)acrylate, cyclohexane diisocyanate denatured urethane di(meth)acrylate, trimethylcyclohexane diisocyanate denatured urethane (meth)acrylate, three Methylcyclohexane diisocyanate denatured urethane (meth) acrylate, aliphatic epoxidized (meth) acrylate , polyfunctional (meth) acrylates such as oligooxyalkyl di(meth) acrylates; triallyl isocyanurate, vinyl (meth) acrylate-13- 200948891, (A A polyfunctional monomer such as allyl acrylate or the like. These ethylenically unsaturated compounds may be used singly or in combination of two or more kinds. The blending ratio of the photosensitive resin (C) is from 10 to 100,000 parts by mass, more preferably from 30 to 1,000 parts by mass, per 100 parts by mass of the recycled PET powder (A). If it is less than 10 parts by mass, its fluidity will decrease, '

Coating or forming becomes difficult and the mechanical strength is lowered. On the other hand, if it exceeds 100,000 parts by mass, it is meaningless and unsatisfactory from the viewpoint of considering the influence on the environment. Q, as the photopolymerization initiator (D), a photopolymerization initiator selected from the group consisting of an oxime ester photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, and a thiophene oxide photopolymerization initiator can be used. One or two or more of the groups. Specific examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXEO1, Irgacure OXE02 manufactured by Ciba Specialty Chemicals Co., Ltd., and N-1919 manufactured by ADEKA Co., Ltd.. Specific examples of the α-aminoacetophenone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2- Benzyl0-dimethylamine-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamine)-2-[(4-methylphenyl) Methyl]-l-[4-(4-morpholinyl)phenyl]-1-butanone, hydrazine, hydrazine dimethylamine phenethyl hydrazine and the like. As a commercially available product, Irgacure 907, Irgacure 369, Irgacure 379, etc., manufactured by Ciba Specialty Chemicals Co., Ltd., may be mentioned as a mercaptophosphine oxide photopolymerization initiator, and specific examples thereof include 2,4,6-trimethyl. Benzylidene diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)--14- 200948891 2,4,4-Trimethyl-pentylphosphine oxide, etc. As a commercial product, Lucirin TPO manufactured by BASF Corporation and Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd. may be mentioned. The blending ratio of the photopolymerization initiator (D) is preferably from 1 to 50 parts by mass based on 100 parts by mass of the photosensitive resin (C). If it is less than 1 part by mass, the photocurability of the copper used for the printed circuit board is insufficient, and the film properties such as peeling of the coating film and chemical resistance are deteriorated. On the other hand, when it exceeds 50 parts by mass, the light absorption under the surface of the solder resist coating film of the photopolymerization initiator (D) becomes intense, and the deep hardenability tends to be lowered. More preferably, it is 55 to 30 parts by mass. Furthermore, as the resin composition for a printed wiring board of the present embodiment, a photopolymerization initiator, a photo-starting agent, a sensitizer, or the like other than the above compounds can be used. For example, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a diphenyl ketone compound, a xanthone compound, a tertiary amine compound, and the like can be given. 〇 Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone. 1,1-dichloroacetophenone and the like. Specific examples of the ruthenium compound include 2-methyl oxime, 2-ethyl oxime, 2-t-butyl fluorene, and 1-chloropurine. Specific examples of the thioxanthone compound include 2,4-dimethylstilbone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropyl. Thio-15- 200948891 tons of ketone and so on. Specific examples of the ketal compound include acetophenone diethyl ketal and benzyl dimethyl ketal. Specific examples of the diphenyl ketone compound include diphenyl ketone, 4-benzyl fluorenyl diphenyl sulfide, 4-benzyl fluorenyl 4'-methyl diphenyl sulfide, and 4-benzyl. Mercapto-4,-ethyldiphenyl sulfide, 4-benzylindolyl-4'-propyldiphenyl sulfide, and the like. Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylamine benzene structure, for example, 4,4′·dimethylamine diphenyl ketone (NissoCure-MABP manufactured by Nippon Soda Co., Ltd.). Dialkylamine diphenyl ketone, 7-(diethylamine)-4-methyl-2H-1-benzoate, etc., such as 4,4'-diethylamine diphenyl ketone (EAB manufactured by Hodogaya Chemical Co., Ltd.) A dialkylamine group such as pyran-2-one (7-(diethylamine)-4 _methylhumoxin) contains a xanthanin compound, 4-dimethylamine benzoic acid ethyl ester (Japanese chemical) Kayacure-EPA, 2-dimethylamine benzoic acid ethyl acetate (Quantacure DMB, manufactured by Internati〇nal Bio-Synthetics, Inc.), 4-methylamine benzoic acid (η-butoxy)ethyl (International Bio- Synthetics) Quantacure BEA), p-methylamine benzoate isoamylethyl ester (Kayacure-DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamine benzoate 2-ethylhexyl ester (Es manufactured by Van Co., Ltd.) 〇丨〇1 507), 4,4'-diethylamine diphenyl ketone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like. Among these compounds, a thioxanthone compound and a tertiary amine compound are particularly preferred. The case of containing thioxanthone compounds is ideal from the point of deep hardenability, in which 2,4-dimethylthioxanthone, 2,4-diethylthioxene-16-200948891 ketone, 2-chloro A thioxanthone compound such as thioxanthone or 2,4-diisopropylthioxanthone is preferred. As the tertiary amine compound, a compound having a dialkylamine benzene structure is preferred, wherein a dialkylamine diphenyl ketone compound having a maximum absorption wavelength of 3 50 to 4 1 Onm containing a dialkylamine group is preferred. Kaempferol compounds are particularly good. As the dialkylamine diphenyl ketone compound, 4,4'-diethylamine diphenyl ketone is preferred, and its toxicity is low. A scopolamine compound containing a dialkylamine 0 group having a maximum absorption wavelength of 350 to 410 nm, because its maximum absorption wavelength is in the ultraviolet field, it is said that the dyeing is small, and it is a colorless and transparent photosensitive composition, and dyeing is used. The pigment becomes a dyed solder resist film that reflects the color of the dyed pigment itself. In particular, 7-(diethylamine)-4-methyl-2H-1-benzopyran-2-one exhibits excellent sensitizing effect with respect to laser light having a wavelength of 400 to 41 Onm. good. The photopolymerization initiator, the photoinitiator, and the sensitizer may be used alone or in combination of two or more kinds. Further, as the carboxyl group-containing resin (E), various resin compounds having a carboxyl group in the molecule may be used. Give alkali developability. In particular, the carboxyl group-containing resin (E) is a photosensitive resin (E -1 ) having a carboxyl group having an ethylenically unsaturated double bond in the molecule, and is photohardenable or developable. Better. Next, it is preferred that the unsaturated double bond is acrylic acid or methacrylic acid or a derivative thereof. As a specific example of the carboxyl group-containing resin (E), the compounds listed below are preferred.尙, (meth) acrylate means a term generally referred to as acrylate, methacrylate and mixtures thereof, and the same is true for other similar -17-200948891. (1) A carboxyl group-containing resin obtained by copolymerization of (meth)acrylic acid and an unsaturated group-containing material. (2) A carboxylic acid-containing urethane resin obtained by addition polymerization of a diisocyanate with a dialohol compound and a diol compound. (3) A photosensitive carboxylic acid formed by addition polymerization of a diisocyanate with a difunctional epoxy (meth) acrylate or a partial acid anhydride denature thereof, a carboxyl group-containing diol compound, and a diol compound A urethane resin. (4) In the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth)acrylic groups in the molecule is contained at the terminal (meth)acrylated carboxylate. Acid urethane resin. (5) In the synthesis of the resin of the above (2) or (3), the (meth)acrylic acid compound having an isocyanate group and one or more (meth)acrylic acid groups in the molecule is contained in the synthesis. Carbamate urethane resin. (6) A photosensitive carboxyl group-containing resin obtained by reacting a bifunctional and polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a diproton acid anhydride to a hydroxyl group of a side chain. (7) The polyfunctional epoxy resin which is epoxidized by epichlorohydrin is further reacted with (meth)acrylic acid to form a bifunctional (solid) epoxy resin, and the resulting hydroxyl group is added. The photoacid anhydride contains photosensitivity -18- 200948891 carboxyl resin. (8) A carboxylic acid-containing polyester resin obtained by reacting a bifunctional oxygen cyclobutane resin with a dicarboxylic acid to form a first-order hydroxyl group to which a diproton anhydride is added. (9) A photosensitive carboxy resin containing a compound having one epoxy group and one or more (meth)acrylic groups in one molecule. By containing such a carboxyl group-containing resin (E), since the side chain of the backbone polymer has a large number of free residues, it is possible to develop by diluting an aqueous alkali solution. Further, the acid value of the carboxyl group-containing resin (E) is preferably from 40 to 200 mgKOH/g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH/g, the dissolution of the exposed portion due to the developing solution proceeds, and the line becomes more than necessary. It is narrow, and depending on the situation, it is impossible to distinguish between the exposed portion and the unexposed portion, and it is dissolved and peeled off in the developing liquid, and the drawing of the normal photoresist pattern becomes difficult. It is preferably 〇45~120mgKOH/g. Further, the weight average molecular weight of the carboxyl group-containing resin (E) varies depending on the resin skeleton, and is generally preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 1,000,000. If the weight average molecular weight is less than 2,000, there is a case where the viscosity is poor, and the moisture resistance of the coating film after exposure is deteriorated, and the film is reduced at the time of development, and the resolution is greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, there is a case where the visibility is remarkably deteriorated, and there is a case where the storage stability is poor. The compounding ratio of the carboxyl group-containing resin (E) is preferably 20 to 60% by mass in the total composition, -19 to 200948891. When the ratio is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when it is more than the above range, the viscosity becomes high and the coating property and the like are lowered. More preferably, it is 30 to 50% by mass. Such a carboxyl group-containing resin may be used singly or in combination of two or more kinds. In addition, as the thermosetting catalyst (F), a thermosetting resin which can promote curing can be used. As such a thermosetting catalyst, specifically, imidazole, 2-methylimidazole, and 2- are mentioned. Ethyl imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2 -imidazole derivatives such as ethyl-4-methylimidazole; dicyanamide, benzyldimethylamine, 4-(dimethylamine)-oxime, fluorene-dimethylbenzylamine, 4-methoxy - an anthracene compound such as hydrazine, hydrazine-dimethylbenzylamine, 4-methyl-hydrazine, hydrazine-dimethylbenzylamine or the like, adipic acid dihydrazine, azelaic acid diterpene or the like; For example, a product such as a triphenylphosphine compound or the like, which is a product of an imidazole compound, which is manufactured by Shikoku Kasei Kogyo Co., Ltd., is commercially available, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ. Name), U-CAT3503N, U-CAT3502T (any trade name of dimethylamine block isocyanate compound) manufactured by San-apro Co., Ltd., DBU, DBN, U-CATSA102, U-CAT5002 (all are Bicyclic guanidine compound and its salt)In particular, 'and limited to these, as long as it promotes the thermosetting catalyst of epoxy resin or oxycyclobutane compound, or the reaction of epoxy group and/or oxycyclobutane group with carboxyl group, such They may be used alone or in combination of two or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-4 can also be used. 6- -20- 200948891 Diamino-S-triazine '2-vinyl-4,6-diamino-S-triazine. Iso-cyanuric acid adduct, 2,4-diamino- An S-triazine derivative such as a 6-methacryl oxiranyloxyethyl-S-triazine·isocyanuric acid addition product, and a compound which can also be used as an adhesion imparting agent and thermosetting Catalyst is better. The mixing ratio of the thermosetting catalyst is usually a sufficient ratio, for example, 0.1 to 20 parts by mass based on 100 parts by mass of the thermosetting component (B) or the carboxyl group-containing resin (E). More preferably, it is 0.5 to 15.0 parts by mass.塡 The chelating agent (G) can be used as needed to increase the physical strength of the coating film. As such a chelating agent (G), an inorganic or organic chelating agent can be used, and in particular, barium sulfate, spheroidal cerium oxide and talc can be suitably used. Further, when it is used for a prepreg, an insulating sheet, or an interlayer insulating layer such as a resin-coated copper foil, a glass cloth or an inorganic or organic fiber nonwoven fabric can be used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, a metal oxide or aluminum hydroxide may be used as a body pigment sizing agent. The compounding ratio of the filler (G) is preferably 75% by weight or less based on the total amount of the composition. When the blending ratio of the enthalpy is more than 75 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, and the coating and moldability are lowered, and the cured product becomes brittle. More preferably, it is 0.1 to 60% by weight. Further, the organic solvent (Η) is used for the synthesis of a thermosetting resin (B), a photosensitive resin (C), a carboxyl group-containing resin (Ε), or the composition of the composition or the molding of the insulating composition. The viscosity is adjusted and used. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and -21 - 200948891 petroleum solvents. . More specifically, ketones such as methyl ethyl ketone and ring; aromatic hydrocarbons such as toluene, hydrazine, and tetramethylbenzene; and soluble, methyl cellosolve, butyl cellosolve, and carbitol are mentioned. Glycol ethers such as methyl carbitol, carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene diethyl ether, triethylene glycol monoethyl ether; acetic acid, acetic acid Ester of butyl ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether ester, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, lactate, ethyl lactate, butyl lactate, etc.; An alcohol such as propanol, ethylene or propylene glycol; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum petroleum brain, hydrogenated petroleum brain or solvent oil. These organic solvents may be used singly or in combination of two or more kinds. Further, any known dye (pigment, dye, or pigment) such as phthalocyanine blue, phthalocyanine, green, iodine, bisazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, or the like can be used. Can be). These dyeing agents are exemplified below. [Cyan dye] Cyan dyes are phthalocyanines and anthraquinones, and pigments are classified into (Pigment) compounds. Specifically, they have a color index (CI; The Society of Dyers and Colourists ) number.

Pigment Blue 15, Pigment Blue 15:1, Pigment Blue, Pigment Blue 15:3, Pigment Blue 15:4, Pigment 15:6, Pigment Blue 16, Pigment Blue 60 'hexanone fiber butyl glycol ethyl acetate acetic acid Methyl diol ether, etc. • Green Conventional Pigment Company 15:2 Blue -22- 200948891 Can be used as a dye system

Solvent Blue 35, Solvent Blue 45, Solvent Blue 63,

Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, and the like. A phthalocyanine compound substituted with or without a metal may also be used in addition to the above. 〇 [Green dye] As a green dye, similarly, there are phthalocyanine, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and so on. A phthalocyanine compound substituted with or without a metal may also be used in addition to these. © [Yellow coloring agent] Examples of the yellow coloring agent include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, and the like. The following are available. Department 醌 蒽

Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193 ' Pigment Yellow 147 ' Pigment Yellow 199, Pigment Yellow 202 -23- 200948891 (isoindolone)

Pigment Yellow 110 , Pigment Yellow 10 9 , Pigment Yellow 139 ' Pigment Yellow 179 ' Pigment Yellow 185 (condensed azo)

Pigment Yellow 93 ' Pigment Yellow 94 ' Pigment Yellow 95, Pigment Yellow 128 ' Pigment Yellow 155 ' Pigment Yellow 166, Pigment Yellow 180 (benzimidazolone)

Pigment Yellow 120 , Pigment Yellow 151 , Pigment

Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181

(monoazo)

PigmentYellowl, 2,3,4,5,6,9,10,12,61,62,62:l,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183, (bisazo system)

PigmentYellowl2,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198 [Red stain] -24- 200948891 As a red stain, there are monoazo and disazo , azo lake system, benzimidazolone, lanthanide, diket〇-pyrrolo-pyrrole, condensed azo, awake, quinacrid 〇ne Specifically, the following may be mentioned. (monoazo)

Pigment Red ❹ 1 , 2,3,4,5,6,8,9,12,14,15,1 6,17,21,22,23,3 1,32,1 12,1 14,146,147,151,170,184,187,188,193,210,245,253,258,266,267,26 8,269, (double azo)

Pigment Red 3 7,3 8,4 1 (single azo lake system) ❿ Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52 :1,52:2,53:1,53:2,57 :1,58:4,63:1,63:2,64:1,68 (benzimidazolone)

Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208 (茈) -25- 200948891

Solvent Red 135, Solvent Red 179, Pigment Red 123,

Pigment Red 149, Pigment Red 166, Pigment Red 17 8,

Pigment Red 179, Pigment Red 190, Pigment Red 194,

Pigment Red 224 (diketopyrrolopyrrole)

Pigment Red 254, Pigment Red 25 5, Pigment Red 264, Pigment Red 270, Pigment Red 272 (condensed azo)

Pigment Red 220, Pigment Red 144, Pigment Red 166,

Pigment Red 214, Pigment Red 220, Pigment Red 221,

Pigment Red 242 Series 0 恵

Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207 (quinacridone)

Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 Others, for the purpose of adjusting the color tone, it is also possible to add a coloring agent such as purple, chrysanthemum, brown or black. Specifically, Pigment Violet 19, -26- 200948891 23, 29, 32 ' 3 6' 38, 42, Solvent Violet 13' 36' CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI

Pigment Orange 3 8 ' CI Pigment Orange 40 ' CI Pigment Orange 4 3 , CI Pigment Orange 4 6 , CI Pigment Orange 4 9 , CI Pigment Orange 5 1 , CI Pigment Orange 6 1 , CI Pigment Orange 63 , CI Pigment Orange 64 , CI Pigment Orange 7 1 , CI

Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 2 5; CI P igm en t B1 ac k 1 , C . I · P i gm ent B1 ack 7 etc. Others, can also be combined with hydroquinone, hydroquinone Thermal polymerization inhibitors such as base ether, t-butylcatechol, gallic phenol, phenothiazine, fine powder of cerium oxide φ, organic bentonite, microcrystalline kaolinite, polyfluorene, fluorine An antifoaming agent such as a polymer or a polymer, a leveling agent, an imidazole imparting agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, or an additive such as a decane coupling agent. In the resin composition for a printed wiring board of the present embodiment, the monomer or a low molecular weight polymer having a certain molecular weight may be dispersed in an organic solvent and used in an uncured state, or may be formed into a resin sheet (film). can. In the case of the unhardened state, for example, the above organic solvent can be adjusted to a viscosity suitable for the coating method, by dip coating, shower coating, roll coating -27-200948891 smearing, roll coating, screen printing A method such as a curtain coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (pre-dried) at a temperature of about 60 to 100 ° C to form a tack-free type. At this time, as a volatile drying, hot air circulating drying oven, IR furnace, heating plate, convection oven, etc., a heat source having a heating method by air generated by steam can be used, and a hot air flow in the dryer can be used. The method of contacting and the method of blowing the nozzle toward the support. Further, in the case of a resin sheet, it can be applied onto a carrier film, and a dry film which is taken up as a film after drying can be applied to a substrate to form a resin layer. Further, it may be a resin-coated copper foil having a dried coating film formed on a copper foil or a semi-hardened prepreg impregnated in a glass cloth. Specific examples thereof include a solder resist, a prepreg, a resin-coated copper foil, a built-up material, an adhesive for a printed circuit board, a top coat for a printed circuit board, a primer for a printed circuit board, and a marking ink. In addition, a resin composition for a photocurable printed circuit board containing a photosensitive resin (C) or the like is cured by light curing. The photohardening can be hardened by various ultraviolet curing devices, ultraviolet exposure devices, or laser light sources, especially light curing devices made of laser light having a wavelength of 550 to 41 Onm. Furthermore, the resin composition for a photocurable thermosetting printed circuit board containing the thermosetting resin (B) can be hardened by heat hardening and hardening. Then, the alkali-developing insulating composition containing the carboxyl group-containing resin (E) can be formed by patterning the light-curing device and then developing the unexposed portion -28-200948891 by diluting an aqueous alkali solution. Graphic type. In this case, as a developing method, a dip method, a shower method, a spray method, a brush method, or the like can be used as the developing liquid, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, or cesium can be used. An aqueous solution of an alkali such as sodium, ammonia or an amine. Hereinafter, the present invention will be specifically described by way of examples. φ [Examples] Hereinafter, the present invention will be further specifically described by examples, but the present invention is not limited to the following examples. In the examples, parts and % are based on quality unless otherwise specified. [Preparation of finely pulverized recycled PET slurry] (Preparation of A-1) The finely pulverized recycled PET (average particle size 25 μmη) produced by Yixing Enterprise was placed in φ. In a jet mill pulverizer, the pulverization pressure was 〇.6 MPa. The condition was carried out twice to obtain a finely pulverized regenerated pet (average particle diameter Ι2 μm) (Α-0). 200 g of the obtained finely pulverized recycled PET (AO) was dispersed in 200 g of propylene glycol monomethyl ether acetate, and then filtered through a mesh of 120×1000 twill weave (nominal filtration precision: about 30 μmη) made of SUS. The regenerated PET slurry (Α-1) was pulverized. At this time, no change was observed in the average particle diameter (modulation of A-2) -29- 200948891 Other than the dispersion of 200 g of finely pulverized recycled PET (A-0) in 200 g of 2-hydroxyethyl methacrylate In the same manner as in Example 1, the finely pulverized recycled PET slurry (A-2) was obtained. At this time, no change was observed in the average particle diameter. [Synthesis of Resin] A cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point) was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a circulation cooling tube, a dropping funnel, and a nitrogen introduction tube. 92 ° C, epoxy equivalent 220 ) 660 g, carbitol acetate 421.3 g, and solvent oil 180.6 g, heated to 90 ° C · stirred and dissolved. Next, after cooling to 60 ° C, 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added, and the mixture was reacted at 10 ° C for 12 hours to obtain an acid value of 0.2 mg KOH / g. Things. To this, 241.7 g of tetrahydrophthalic anhydride was added, and the mixture was heated to 90 ° C to cause a reaction for 6 hours. Thereby, an acid value of 50 mgKOH/g, a double bond equivalent (g weight of the unsaturated group per 1 mol of the resin) 400, a carboxyl group having a weight average molecular weight of 7,000, and a photosensitive resin (E-1) solution were obtained. Preparation of the components The components shown in Table 1 were mixed, premixed in a blender, and kneaded by using three roll mills to prepare the resin compositions of Examples 1 to 5. The degree of dispersion of the resin composition obtained herein was measured by particle size measurement by a particle size analyzer manufactured by Erichsen Co., Ltd., and was evaluated to be 3 μm or less. 200948891 [Table 1]

Example 1 Example 2 Example 3 Example 4 Example 5 A component Α-1 40 30 40 30 Α-2 40 B component JER828 *1 100 ΕΡΡΝ-201 *2 15 15 ΥΧ-4000 *3 30 30 HP4032D * 4 140 TD-2106 *5 100 ΥΡ-50 *6 10 C component DPHA *7 20 20 D component Irg907 *8 10 10 DETX *9 1 1 EAB *10 0.1 E component E-1 154 154 F component 2PHZ-PW * 11 1 dicyanamide 3 0.3 0.3 2MZ-A *12 3 melamine 3 3 G component B-30 *13 20 50 talc 10 cerium oxide 10 micro powder cerium oxide 3 3 3 UVR-150G *14 100 Η component DPM *15 Dyeing pigment phthalocyanine blue 0.5 0.5 0.5 Dyeing pigment AGR *16 0.3 0.3 0.3 Defoamer polyfluorene defoamer 3 3 3 Σ 169 140 316.4 286.3 291 Remarks *1 Double acid A type epoxy resin (Japan Epoxy Resin *2 Phenolic novolac type epoxy resin (manufactured by Nippon Kasei Co., Ltd.) *3 Epoxy resin (Japan^) 〇xyResin) *4 Epoxy resin, epoxy equivalent 145 (Daily Ink Chemical Industry) )) *5 phenol novolac resin (large Japanese ink Industrial Co., Ltd. *6 phenoxy resin (manufactured by Tohto Kasei Co., Ltd.) *7 Dipentaerythritol hexaacrylate (manufactured by Sakamoto Chemical Co., Ltd.) *8 2-Methyl-1-[4-(methylthio)phenyl]-2- Morpholinylacetone-1 *9 2,4-diethylthioxanthone*10 Diethylamine diphenyl ketone* 11 2-phenyl*4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei) * 12 2,4-Diamino-6-[ 2'-methylimidazolyl]-(Γ )]-ethyl-s-triazine (manufactured by Shikoku Chemicals Co., Ltd.) *13 Barium sulfate (manufactured by Nippon Chemical Co., Ltd.) * 14 UV curable solder resist ink (made by Sun Ink) *15 Dipropylene glycol methyl acid acetate vinegar *16 Yellow pigment (Chlomophthal AGR: trade name) _ -31 - 200948891 [Evaluation of resin composition 1] (Production of test piece) With respect to each of the resin compositions of Examples 1 to 4 thus obtained, a copper-clad laminate FR-4 substrate each having a circuit formation was used as a substrate (for evaluation of solder heat resistance), and an IPC B-25 comb-type electrode B was formed. A copper-clad laminate (for electrical insulation evaluation) of the sample was prepared as follows. The resin composition of Example 1 was formed by coating a mesh of a PET 150 mesh on a thickness of 20 μm on each substrate, and thermally hardening it by heating at 150 ° C for 30 minutes in a hot air circulating drying oven. Test piece. The resin composition of Example 2: a thickness of 15 μm was applied to each substrate by a mesh screen of PET225 mesh, and transferred by a conveyor at a speed of 4 m/min while being air-cooled by 80 W. A 3 mm high-pressure mercury lamp of /cm was irradiated with ultraviolet rays to prepare a test piece. The resin compositions of Examples 3 and 4 were coated with a PET 100 mesh screen on each substrate to a thickness of 20 μm, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes to form no Sticky film. The substrate was placed on a negative film, exposed as in the desired pattern, and developed by punching 2 kg/cm 2 of an aqueous solution of 1 wt% Na 2 CO 3 to form a photoresist pattern. This substrate was heated and cured at 150 ° C for 60 minutes to prepare a test piece. (Performance evaluation) The test piece produced in this way was evaluated for the following items. -32-200948891 <Pressure heat resistance> The resin composition of Examples 1 to 4 was coated with a rosin-based flux on each test piece prepared by using a circuit-formed copper-clad laminate FR-4 substrate, and heated in advance. After immersing in a flux bath of 260 ° C for 30 seconds, the flux was washed with propylene glycol monomethyl ether, and the swelling, peeling, and discoloration of the photoresist layer were visually evaluated. The evaluation results are shown in Table 2.尙, as follows, n 〇: No change at all △: Some slight change X: The film is swollen and peeled off. <Electrical Insulation> The comb-shaped φ electrode of each of the test pieces prepared by using the resin composition of Examples 1 to 4 and the copper-clad laminate formed using the IP C B-2 5 comb-type electrode B sample was A bias voltage of DC 5.5 V was applied, and the insulation resistance 后 after being placed at a humidity of 85% and a temperature of 130 ° C for 150 hours was measured. The evaluation results are collectively shown in Table 2. [Table 2] Example 1 Example 2 Example 3 Example 4 Heat resistance of solder 〇〇〇〇 Electrical insulating property 1 χ 1012 Ω or more lxlOuQ or more 1 χ 1012 Ω or more 1 χ 1012 Ω or more As shown in Table 2, it was found that good solder heat resistance was obtained. , also -33- 200948891 can obtain high electrical insulation. [Evaluation 2 of Resin Composition] (Production of Sample for Evaluation) The compounding component of Example 5 shown in Table 1 was further added with propylene glycol monomethyl ether acetate and AER0SIL #972 of bismuth dioxide. The organic solvent was kneaded and dispersed in three light mills to obtain a thermosetting resin composition having a viscosity adjusted to 40 dPa·s ± 10 dPa·s (rotational viscometer 5 rpm, 25 ° C). Next, the obtained thermosetting resin composition was adjusted to a viscosity of 1 to 2 dPa_s using methyl ethyl ketone to prepare a coating varnish. Each of the obtained coating varnishes was applied to a rough surface of a 18 μm thick copper foil (F3-WS: manufactured by Furukawa CIRCUIT FOIL Co., Ltd.) using a dye tank, and the film thickness of the dried coating film was 60 μm, at 40 to 12 CTC. Drying to obtain a resin-attached copper foil. The resin copper foil at this time has a gelation time of 60 seconds to 90 seconds at 1 70 °C. Next, the two resin-attached copper foils thus obtained were directly pasted so that the resin surface became the inner side. The hot press was subjected to a hot press at 120 ° C, 5 kgf/cm 2 for 30 minutes, and further at 170 ° C. It is thermohardened in 2 hours and is integrally formed. Then, this is done directly, or the copper foil is etched to prepare a hardened film sample for physical property measurement. Further, an inner layer circuit was formed by a copper foil 18 μm thick glass epoxy double-sided copper-clad laminate, and the resin-coated copper foil was adhered to both sides of the substrate treated with MECetch BOND of Mec Corporation, and the hot press was used at 5 kgf. /cm2, 20 minutes at 120 ° C, followed by hardening under conditions of 25 kgf / cm 2 , 2009 48891 1 70 ° C for 2 hours to form a laminate. Further, at a predetermined position of the laminate, the through hole portion is formed by opening the drill bit. Further, first, a resist is used to selectively remove the copper foil from the hole position, and then a guide is provided, and a laser perforated portion is formed by opening a hole by a laser processing machine. Then, after the through hole portion and the laser perforated portion are removed by the desmear treatment, the conductive hole portion is formed by etching through a commercially available resist by electroless copper plating and electrolytic copper plating. The pattern is made into a multilayer printed circuit board sample. (Performance evaluation) For the evaluation samples prepared in this way, the following two items were evaluated. <Peel strength> 测定 Measurement was carried out in accordance with JIS C648 1. <Solder Heat Resistance> The completed printed circuit board (10 cm x 10 cm) was immersed in a solder layer of 288 t: ± 3 t: for 10 seconds. Then, after repeating this operation five times, the peeling of the copper foil and the resin was confirmed.尙, such as the following 〇: no peeling X: peeling -35- 200948891 as the evaluation standard. <Pattern Formability> The peeling of the circuit of the line and the space of 75 μm / 75 μm was visually inspected.尙 , such as the following 无: no peeling X: peeling is used as the evaluation standard. [Table 3] Example 5 Peel strength 10.2 N/cm Flux heat resistance 〇 Pattern formation property 〇 As shown in Table 3, it was found that good solder heat resistance and pattern formation properties were obtained in addition to high peel strength. Still, the present invention is not limited to the above embodiments. Others may be implemented without departing from the scope of the gist thereof. -36-

Claims (1)

200948891 VII. Patent application scope: 1. A resin composition for a printed circuit board, characterized in that it contains regenerated polyethylene terephthalate (A). (2) The resin composition for a printed circuit board according to the first aspect of the invention, which is prepared by mixing a regenerated poly(p-citric acid) ethylene phthalate fine powder having an average particle diameter of 0.1 to 15 μm. 3. The resin H composition for a printed circuit board according to the first aspect of the invention, wherein the regenerated polyethylene terephthalate (Α) is 0·1 to 7 5 % of the total amount. 4. The resin composition for a printed circuit board according to the first aspect of the invention, which contains a thermosetting resin. 5. The resin composition for a printed circuit board according to claim 1, wherein the photosensitive resin (C) is contained. A dry film comprising a coated resin film of a resin composition for a printed circuit board according to any one of the first to fifth aspects of the invention. 7. A printed circuit board comprising: a substrate on which a circuit is formed, and at least a portion of the substrate is formed in any one of claims 1 to 5; A permanent film of a printed circuit board hardened with a resin composition. 8. A printed circuit board characterized by having a substrate on which a circuit is formed, and at least a portion of the substrate on the substrate is made by the dry film described in the patent application No. 6-37-200948891 Transfer of the coated film after hardening of the permanent film -38- 200948891 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure·· -3- 200948891 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none