TWI659986B - Resin-containing sheet, structure and wiring board using the same - Google Patents

Abstract

Provided is a resin-containing sheet that improves the mechanical strength of a fibrous base material and improves the adhesion to a substrate, and a structure and a wiring board using the same.

The resin-containing sheet of the present invention includes: a fiber substrate (11); a fixing agent (2) for fixing the fibers (1) in the fiber substrate (11) to each other; and contacting the fiber substrate (11) The storage modulus of the resin (3) with the fixing agent (2) is higher than that of the resin (3). The structure obtained by making this resin-containing sheet adhere to a board | substrate. A wiring board having this structure.

Description

Resin-containing sheet, structure and wiring board using the same

The present invention relates to a resin-containing sheet having excellent mechanical strength, modulus, and adhesion, and is suitable for a wiring board for an electronic device, and a structure and a wiring board using the same.

As a wiring board for electronic equipment, generally, a prepreg obtained by impregnating a resin such as epoxy with a substrate made of glass fiber, aramid fiber, cellulose fiber, or the like ( A semi-cured resin insulation layer), the prepreg is adhered to a metal foil such as copper, and a circuit is formed by an etching method. In addition, the wiring board is provided with a solder resist to prevent outflow of solder during component mounting. Wiring board materials such as prepreg or solder resist must adhere to the wiring board surface on which the metal foil surface or circuit has been formed without gaps, and then heat and press them to make them adhere. The closeness will be important. In addition, in order to improve mounting reliability, high strength (high modulus) is desired for a wiring board, and prepregs or solder resists of the constituent members are similarly attempted to have a high modulus.

Regarding the conventional technical aspects of wiring board materials, for example, Patent Document 1 describes a prepreg which is used to obtain insulation reliability and The two functions of stress relaxation of the wiring are provided with resin layers having different strengths (modulus) on both sides of the core layer. However, this technique is to provide different resin composition layers on both sides of the core layer, and it does not disclose what is useful for adhesion. Further, Patent Document 2 describes a prepreg having a predetermined modulus. This technology aims at the temporary fixation of the prepreg sheet and the circuit board to control the modulus by the composition.

Furthermore, Patent Document 3 discloses a technique of using two types of resin compositions in a prepreg. In this prepreg, the two kinds of resin compositions are locally present so that the modulus closer to the surface side becomes larger. Further, Patent Document 4 describes a technique for providing an adhesive layer on the surface of a prepreg, which is for improving the adhesiveness to a metal foil.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-088280

[Patent Document 2] Japanese Patent Laid-Open No. 2006-179716

[Patent Document 3] Japanese Patent Laid-Open No. 2010-095557

[Patent Document 4] Japanese Patent Laid-Open No. 2004-168943

However, the above-mentioned conventional prepregs still do not have sufficient mechanical strength and adhesion.

Here, an object of the present invention is to provide a resin-containing sheet having improved mechanical strength and improved adhesion to a substrate, and a structure and a wiring board using the same.

As a result of intensive studies to solve the above-mentioned problems, the inventors have found the following.

That is, generally, in woven or non-woven fabrics composed of various fibrous materials, fibers are entangled or interact to form aggregates. Therefore, as shown in FIG. 2 (a), when a tension T is applied to such an assembly of fibers 21 in one direction, the fibers 21 will slide at the contact point P, and the fibers 21 will extend along the arrow D. The direction will be pulled apart, the assembly will burst, and will eventually break. At this point, in the case of woven fabrics, the strength in the fiber direction for stretching is a certain height, but the strength in the direction different from the fiber direction (oblique direction) for stretching is low. In the case of a non-woven fabric, the tensile strength is low in any direction.

As described above, wiring boards are made of prepregs made of woven fabrics (such as glass cloth) or non-woven fabrics (such as those made of polyaramide fibers) and resins. It is important to ensure the strength of the wiring board and prevent the fibers from sliding against each other in the fiber assembly. On the other hand, as described above, the resin-containing sheet is also required to have good adhesion to the surface of the metal foil or the surface of the wiring board.

As a result of the above review, the inventors found that by setting The following structure can achieve a balance between mechanical strength and adhesion.

That is, the resin-containing sheet of the present invention is characterized by comprising: a fiber substrate; a fixing agent for fixing fibers in the fiber substrate; a resin contacting the fiber substrate and the fixing agent; The storage modulus of the agent is higher than the storage modulus of the aforementioned resin.

In the present invention, the glass transition temperature of the fixing agent is preferably higher than the glass transition temperature or softening temperature of the resin. The resin-containing sheet of the present invention can be obtained by impregnating the fibers of the fibrous base material with a fixing agent composition and then impregnating the fixed fiber base material with the resin composition. In this case, the viscosity of the anchor composition is preferably 1 Pa · s or less. In the resin-containing sheet of the present invention, it is preferable that the fibrous substrate is a woven fabric or a non-woven fabric.

The structure of the present invention is characterized in that the resin-containing sheet of the present invention described above is adhered to a substrate.

Furthermore, the wiring board of the present invention is characterized by having the structure of the present invention described above.

According to the present invention, a resin-containing sheet having improved mechanical strength and improved adhesion to a substrate can be obtained. That is, in the present invention, it was found that "by setting the storage modulus of a fixing agent (which is used to fix the fibers in the fibrous substrate to each other) to a resin (which is used to contact the fiber substrate and "The storage modulus of the fixing agent is high." This is used to obtain resin-containing sheets that are intended to achieve high strength and high modulus, while improving adhesion. Material conditions. In this system, high strength is required for resin insulation materials for wiring boards. However, for example, when a high-modulus material such as polyimide is used, the adhesion to metal foils and the like is deteriorated. At the same time of modularization, it also solves the problem of adhesion.

1, 21‧‧‧ fiber

2‧‧‧ Fixing agent

3‧‧‧ resin

11‧‧‧ fiber substrate

P‧‧‧Contact

D‧‧‧ Direction of fiber being pulled apart due to tension T

S‧‧‧ space

[Fig. 1] An explanatory view showing the structure of the resin-containing sheet of the present invention in a simulated manner.

[Fig. 2] An explanatory diagram showing the behavior (a) and (b) where the fibers are not fixed to each other when the fibers T are applied with a tension T in one direction.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

The explanatory diagram shown in FIG. 1 shows the structure of the resin-containing sheet of the present invention. The resin-containing sheet of the present invention is mainly a sheet-like body formed of a fiber component and a resin component. As shown in the figure, the resin-containing sheet has a "fiber base material 11", "Reagent 3" and "Resin 3" in contact with the fibrous substrate 11 and the fixing agent 2. In addition, the symbol S in the figure represents a space in which neither the fixing agent 2 nor the resin 3 is impregnated in the fiber base material 11. In the resin-containing sheet of the present invention, the fiber 1, the fixing agent 2, and the resin 3 constituting the fiber base material 11 can be regarded as a whole. One layer is formed. In the resin-containing sheet of the present invention, it is important that the storage modulus of the fixing agent 2 that fixes the fibers 1 to each other is higher than the storage modulus of the resin 3 at any temperature.

That is, as a result of intensive research, the present inventors found that the resin component contained in the resin-containing sheet has two roles: the first role is to suppress the fibers from sliding with each other, and is used to increase the strength and modulus of the resin-containing sheet. It acts as a fixing agent; the other role is to make the insulating resin layer and the surface of the metal foil adhere to each other. Based on such a point of view, the inventors further reviewed the results and found that the two roles of the resin component contained in the resin-containing sheet are shared separately, and the high-strength guarantee is that the role is shared by the fixing agent. The guarantee of adhesion is to share the role with the resin. By specifying the relationship between the fixing agent and the storage modulus of the resin, it can be ensured that the two properties are good at the same time. In this way, the role of the resin component is divided into two types, which can have both high modulus and good adhesion. This technology has never been seen before.

As shown in FIG. 2 (b), when the present invention is conceptually described, the contact point P of the fiber 1 included in the fiber base material 11 is fixed by the fixing agent 2, even if it is When tension T is applied in the direction, sliding does not occur at the contact point P, so that the fiber substrate 11 can have high strength and high modulus. Furthermore, by impregnating the resin 3 with the fiber substrate 11 and the fixing agent 2 in contact with each other, it is possible to obtain a resin-containing sheet having good adhesiveness. Therefore, according to the resin-containing sheet of the present invention, the high modulus required for the fibrous base material 11 can be secured by the fixing agent 2 and the adhesiveness to the substrate or the like can be secured by the resin 3. By using poly A resin-containing sheet having both high strength and good adhesion that cannot be obtained with a high modulus material such as imine.

[Fiber substrate]

The fiber base material 11 according to the present invention is composed of an aggregate of fibers 1. The fiber 1 is not particularly limited as long as it can form aggregates and produce woven or non-woven fabrics. Natural fibers or chemical fibers can be mainly used. Among the specific examples of the fiber 1, examples of the natural fiber include glass fiber, cellulose fiber, rock fiber, metal fiber, carbon fiber, and rock wool. Examples of the chemical fiber include polyaramide, nylon, vinylon, and nylon. Ethylene, polyester, polyolefin (polyethylene terephthalate, modified polyethylene terephthalate, polyethylene, polypropylene, etc.), polyurethane, acrylic, polyvinyl chloride, poly Ether ether ketone, polyfluorene, imine, polyphenylene sulfide, polyether, imine, polytetrafluoroethylene, acetate, triacetate, Promix, fluorene, copper ammonia , Lyocell, Tencel, etc. Among these, one type may be used alone or two or more types may be used in combination. In addition, the manufacturing method, fiber content (fiber blending ratio), fiber diameter, fiber length, mass (weighing amount), density (specific gravity), thickness, and woven structure of the woven fabric can be appropriately selected according to the purpose. As the fiber base material 11, among the above, from the viewpoint of the affinity with the fixing agent, glass fiber, cellulose fiber, and polyamide fiber are preferred.

In the present invention, it is particularly preferable to use a woven fabric as the fiber base material 11 and by weaving, even if the fiber is originally low in strength, the advantage of high strength can be obtained. In the present invention, as the fiber base material 11, When using glass fibers that are not originally high strength, but when using organic fibers with low strength, the use of a fixing agent with a high storage modulus also has the advantage of high strength.

[Fixing agent composition]

As the anchoring agent composition forming the anchoring agent 2, as long as it is capable of adhering to the fibers 1 and fixing the fibers 1 to each other, only the contact portion where the fibers are bonded to each other may be an anchor or a coating. The whole of Fiber 1 and its anchor. The amount of the anchoring agent composition used may be such an amount that the fibers 1 can be fixed to each other and not adversely affect the adhesiveness. The fiber 1 is fixed by the fixing agent 2. In the collected aggregate, the volume ratio of the fiber 1 to the fixing agent 2 is calculated in the solid content after the organic solvent is removed, and the range of 99: 1 to 50:50 is particularly preferable. When the volume ratio of the fibers 1 and the fixing agent 2 is within this range, the fibers 1 can be sufficiently fixed to each other by the fixing agent and obtain a desired high strength, and at the same time, by impregnation of the resin 3 afterwards, It is preferable to ensure good adhesion. In particular, the amount of the fixing agent 2 used is preferably an amount that does not cause a substantial change in the film thickness of the fiber base material 11 before and after the application of the fixing agent 2. Here, the so-called "substantially no change in film thickness" means that the fiber substrate 11 swells and increases the apparent thickness due to the solvent component of the fixing agent composition, and is excluded from the "film thickness" Change ". The anchoring agent composition is preferably a liquid when it is adhered to the fibers, and it can be made liquid by changing the temperature or pressure for the user. In particular, the rotor composition is rotated at 25 ° C and E-type viscosity. The viscosity measured at 5 rpm is 1 Pa · s or less, for example, 1 ~ 0.0001 Pa · s is preferred. By this, the fixing agent composition can be impregnated into the inside of the aggregate of the fibers 1, and the fibers can be made more stable with each other. For fixation.

The anchoring agent composition is one that is cured by heat or light. The so-called "hardening" here means that a liquid is chemically changed into a solid by the energy of heat or light. As an anchoring agent composition, conventional components can be used according to the use, and it can use it individually by 1 type or in combination of 2 or more types. Examples of conventional components used in the fixing agent composition include a thermosetting resin, a hardener, a thermosetting catalyst, a photocurable resin, a photopolymerization initiator, a photoacid generator, a photobase generator, and the like. As the organic solvent, specifically, those shown below can be used.

(Thermosetting resin)

The thermosetting resin may be any resin that is hardened by heating and exhibits electrical insulation properties, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol S type epoxy resin. Bisphenol E epoxy resin, bisphenol M epoxy resin, bisphenol P epoxy resin, bisphenol Z epoxy resin, bisphenol epoxy resin, bisphenol A novolac epoxy resin, phenol Novolac epoxy resin, novolac epoxy resin, novolac epoxy resin, biphenyl epoxy resin, biphenylaralkyl epoxy resin, aryl alkylene epoxy resin, etc. Tetrahydroxyphenylethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin Resin, adamantane type epoxy resin, fluorene type epoxy resin, shrink Water glyceryl methacrylate copolymer epoxy resin, epoxy resin copolymerized with cyclohexyl maleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative, CTBN Modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexane Glycol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) cyanurate, triglycidyl Novolac-type phenolic resins such as tris (2-hydroxyethyl) cyanurate, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, and unmodified resol phenol ) Resin, phenolic resin such as resole phenolic resin modified with tung oil, linseed oil, walnut oil (Macadamia Oil) and other oil-modified resole phenolic resin, phenoxy resin, urea ( urea) resin, melamine resin, and other resins containing triazine ring resin, unsaturated polyester resin, and bismaleimide resin Diallyl phthalic acid resin, silicone resin, resin having an oxazine ring, norbornene-based resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, malay Perylene imine resin, bismaleimide imine triazine resin, polyazomethine resin, polyimide resin, and the like. Among these, an epoxy resin or a polyimide resin is particularly preferred because it has excellent reliability as an insulating layer.

As the epoxy resin, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin can be liquid or solid or semi-solid. Among them, bisphenol A epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, or a mixture of these It is better. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the epoxy resin include, but are not limited to, jER828 manufactured by Mitsubishi Chemical Corporation.

When an epoxy resin is used to form a cured product, it is preferable to contain a curing agent in addition to the epoxy resin. As the hardener, 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), etc. can be used. Imidazole-based hardeners, ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, m-xylylenediamine, isophoronediamine, norbornenediamine, 1, Amine hardeners such as 3-bisaminomethylcyclohexane, N-aminoethylpiperazine, polyamine, vinylphenol, aralkyl-type phenol resin, phenolphenylaralkyl resin, phenol Phenol-based hardeners such as benzoaralkyl resins, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalate Formic anhydride, methylnadic anhydride, dodecyl succinic anhydride, chloric anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (trimellitic anhydride), methylcyclohexene tetracarboxylic acid Known hardeners such as acid anhydride-based hardeners such as acid anhydrides, cyanate resins, active ester resins, aliphatic or aromatic primary or secondary amines, polyamine resins, and polythiol compounds. The blending amount of the hardener is preferably 0.1 to 150 parts by mass, and more preferably 0.5 to 100 parts by mass, relative to 100 parts by mass of the epoxy resin. By setting the blending amount of the curing agent to 0.1 parts by mass or more, the resin composition can be sufficiently hardened. By setting the blending amount to 150 parts by mass or less, an effect corresponding to the blending amount can be efficiently obtained.

Examples of the thermosetting catalyst include imidazole, 2- Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 -Cyanoethyl) imidazole derivatives such as 2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4- (dimethylamino) -N, N- Amine compounds such as dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, dihydrazide adipate Hydrazine compounds such as dihydrazine sebacate; phosphorus compounds such as triphenylphosphine. It is also possible to use guanoamine, ethinoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and the like. -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine‧isocyanuric acid adduct, 2,4-diamine- S-triazine derivatives such as 6-methacryloxyethyl-S-triazine and isocyanuric acid adducts.

Examples of the polyimide resin include those obtained through a synthetic reaction of an aromatic polycarboxylic anhydride or a derivative thereof generally known with an aromatic diamine, and obtained through a polyimide acid (polyimide precursor). And the polyamidic acid composition is a so-called commercially available polyimide varnish in a state of being dissolved in an organic solvent.

Specific examples of the aromatic polycarboxylic anhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'- Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2- Bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic acid Acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc. These can be used alone or in combination of two or more. Among these, it is particularly preferable to use pyromellitic dianhydride as at least one of the components.

Specific examples of the aromatic diamine that reacts with a polycarboxylic acid such as an aromatic polycarboxylic anhydride include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, and m-aminobenzylamine. , P-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis ( 3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) Sulfide, (3-aminophenyl) (4-aminophenyl) fluorene, bis (3-aminophenyl) fluorene, (3-aminophenyl) (4-aminophenyl) fluorene , Bis (4-aminophenyl) fluorene, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminobenzene (Oxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1 , 1-bis [4- (4-aminophenoxy) phenyl] -ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2- Bis [4- (4-aminophenoxy) Yl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) benzene Group] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl , 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] one, bis [4- (4-aminophenoxy) Phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3- Aminophenoxy) phenyl] fluorene, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (4-aminophenoxy) phenyl] hydrazone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl ] Ether, 1,4-bis [4- (3-aminophenoxy) benzyl) benzene, 1,3-bis [4- (3-aminophenoxy) benzyl) benzene 4,4'-bis [3- (4-aminophenoxy) benzylidene] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzidine Group] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino -α, α-dimethylbenzyl) phenoxy] diphenylfluorene, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] fluorene, 1,4-bis [4- (4-aminophenoxy) phenoxy] -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α -Dimethylbenzyl] benzene and the like. These can be used alone or in combination of two or more. Among them, it is particularly preferable to use 4,4'-diaminodiphenyl ether as at least one of the components.

Examples of polyimide varnishes include RIKACOAT SN20, RIKACOAT PN20, RIKACOAT EN20, TORAYNEECE made by Toray (stock), U-varnish, and JSR (stock) OPTOMER, Nissan Chemical Co., Ltd. SE812, Sumitomo Bakelite (shares) CRC8000.

The polyamidic acid solution obtained by the synthesis reaction or a commercially available polyamidic acid solution may be treated by heating or the like to cyclize (polyimine) the polyamidic acid into a polyamidoimine. . Polyimide can be fluorinated by heating alone or chemically. In the case of heating only, polyimide can be imidized by heat treatment at, for example, 200 to 350 ° C. In addition, the chemical method is a method in which polyimidization can be performed quickly, and polyamidic acid can be heat-treated at the same time using an alkaline catalyst, which is a method capable of complete imidization. The basic catalyst is not particularly limited, and conventionally known basic catalysts can be used, and examples thereof include pyridine, diazinebicycloundecene (DBU), diazinecyclononene (DBN), and various tertiary amines. These alkaline catalysts can be used alone or in combination of two or more.

(Photocurable resin)

As the photocurable resin, any resin that hardens and exhibits electrical insulation properties by irradiation with active energy rays may be used, and it is particularly preferable to use a compound having one or more ethylenically unsaturated bonds in the molecule. As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like can be used.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. Examples of the (meth) acrylate-based oligomer include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (Meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) ) Acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like. In addition, in this specification, a (meth) acrylate is a term collectively referred to as an acrylate, a methacrylate, and a mixture thereof, and it is the same also about other similar descriptions.

As the photopolymerizable vinyl monosystem, a styrene derivative such as styrene, chlorostyrene, α-methylstyrene, or the like; vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl esters; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl-n- Octyl alkyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether and other vinyl ethers; acrylamide, methacrylamide, N -Hydroxymethacrylamide, N-Hydroxymethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamine, N-butoxymethacrylamine (Meth) acrylamidoamines such as amines; allyl compounds such as triallyl cyanurate, diallyl phthalate, diallyl isophthalate, etc .; 2-ethylhexyl (Meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isofluorenyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (Methyl) (Meth) acrylic acid esters such as acrylates; hydroxyalkyl (meth) groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate ) Acrylic esters; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. (Meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediene Alkyl polyols such as alcohol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Acrylate); diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylol Polyoxyalkylene glycols such as propane tri (meth) acrylate, poly (meth) acrylates; Pivalic acid, neopentyl glycol di (meth) acrylate, etc. Poly (meth) acrylates; cyanurate-type poly (meth) acrylates, such as tri [(meth) acryloxyethyl] cyanurate, and the like.

As a photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, etc. can also be used suitably. Among them, alicyclic epoxy compounds include, for example, 3,4,3 ', 4'-diepoxydicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2- Bis (3,4-epoxycyclohexyl) -1,3-hexafluoropropane, bis (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxy Cyclohexyl)] ethylbenzene, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) ring Hexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3 ', 4'-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2- Bis (3,4-epoxycyclohexanecarboxylic acid) ester, Cyclohexene epoxide, 3,4-epoxycyclohexylmethanol, 3,4-epoxycyclohexylethyltrimethyl Alicyclic epoxy compounds having an epoxy group, such as oxysilane.

As oxetane compounds, except for bis [(3-methyl-3- Oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, acrylic acid ( 3-methyl-3-oxetanyl) methyl ester, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetan) methacrylic acid Other than polyfunctional oxetanes such as butane) methyl ester, (3-ethyl-3-oxetanyl) methacrylate, or oligomers or copolymers thereof, Also available are oxetanol and novolac resins, poly (p-hydroxystyrene), cardo type bisphenols, calixarenes, resorcinol calixarene (calixresorcinarene) ), Or etherates of resins having a hydroxyl group, such as silsesquioxane, and oxetane, such as a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate Compound.

Examples of the vinyl ether compounds include cyclic ether vinyl ethers (such as an ethylene oxide ring and an oxetane ring) such as isosorbide divinyl ether and oxanorbornene divinyl ether. , Oxane rings and other vinyl ethers with cyclic ether groups); aryl vinyl ethers such as phenyl vinyl ether; alkyl groups such as n-butyl vinyl ether and octyl vinyl ether Vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexane Polyfunctional vinyl ethers such as dimethanol divinyl ether; vinyl ether compounds having a substituent such as an alkyl group or an allyl group at the α and / or β position; and the like. Examples of commercially available products include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), and 2-hydroxybutyl vinyl ether (HBVE) manufactured by Maruzan Petrochemical Co., Ltd. , Triethylene glycol divinyl ether, etc.

When using a photocurable resin, in addition to the photocurable resins described above, a photopolymerization initiator, a photoacid generator, a photobase generator, etc. may be used. One of these may be used alone, or two of them may be used in combination. Used above.

Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; phenethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Ketones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinylphenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Phenyl] -1-butanone and other amino alkylacetophenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-third butylanthraquinone, 1-chloroanthraquinone, etc. Quinones; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc .; Acetophenone dimethyl ketals, benzyl dimethyl ketals and other ketals; benzophenones and other benzophenones; or xanthone ketones; (2,6-dimethoxybenzene (Methylamidino) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6-trimethylbenzene Formamidine diphenylphosphine oxide, Phosphine oxides such as ethyl-2,4,6-trimethylbenzylidenephenyl phosphonate; various peroxides, ferrocene-based initiators, oxime ester-based initiators, etc. These are compatible with ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethyl A tertiary amine light sensitizer such as amine, triethanolamine and the like are used in combination. These photopolymerization initiators can be used alone or in combination of two or more.

Examples of the photoacid generator include onium salts such as diazonium salts, sulfonium salts, bromium salts, chloronium salts, sulfonium salts, selenium salts, pyranium salts, thianium salts, and pyridinium salts; Tris (trihalomethyl) -s-triazine (e.g. 2,4,6-tris (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethylene Group] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s -Halogenated compounds such as triazines; 2-nitrobenzyl esters of sulfonic acids; iminosulfonates; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N- Hydroxyfluorenimine = sulfonate; tris (methanesulfonyloxy) benzene derivative; bissulfonyl diazomethanes; sulfonylcarbonyl alkanes; sulfonylcarbonyldiazomethanes; difluorene compounds Iron heavy ene complex, etc. These photoacid generators can be used alone or in combination of two or more.

A photobase generator is a compound whose molecular structure is changed by irradiation with light such as ultraviolet rays or visible light, or when one or more molecules are cracked to produce one or more basic substances that can function as catalysts for polymerization reactions. . Examples of the basic substance include a secondary amine and a tertiary amine. Examples of such a photobase generator include an α-aminoacetophenone compound or an oxime ester compound, a fluorenyloxyimine group, an N-formamated aromatic amine group, and an N-fluorinated group. Compounds of substituents such as an aromatic amino group, a nitrobenzylcarbamate group, and an alkoxybenzylcarbamate group. These photobase generators can be used alone or in combination of two or more.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and aromatics such as toluene, xylene, and tetramethylbenzene. Hydrocarbons; methyl cyrus, ethyl cyrus, butyl cyrus, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Glycol ethers such as propylene glycol monoethyl ether, triethylene glycol monoethyl ether, and the like; ethyl acetate, butyl acetate, celex acetate, diethylene glycol monoethyl ether acetate, and the above Esters such as glycol ether esters; alcohols such as methanol, propanol, ethylene glycol, and propylene glycol; 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazoline Ketone, 2-pyrrolidone, ε-caprolactam, formamidine, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, etc. Amines; ethers such as tetrahydrofuran and dioxane; nitriles such as acetonitrile, benzonitrile, and propionitrile; chloroform, dichloromethane, bromobenzene, dibromobenzene, chlorobenzene, and dichlorobenzene; N-methyl-2-pyrrolidone, dimethylaniline, dibutylaniline, diisopropylaniline and other amines; sulphur compounds such as dimethyl sulfene and cyclobutane; octane, decane, etc. Aliphatic hydrocarbons; petroleum ether, naphtha, hydrogenated naphtha, petroleum solvents Petroleum-based solvents and the like. Among these, N-methyl-2-pyrrolidone or methyl ethyl ketone is easier to handle, so it is preferable.

[Resin composition]

In the resin-containing sheet of the present invention, the resin 3 is one that is in contact with the fixing agent 2 and the fiber substrate 11. In the present invention, as long as the resin 3 can fulfill the role of ensuring adhesion, it may be coated on the outer side of the fiber base material 11. The impregnation rate of the resin composition is not particularly limited as long as it allows the resin-containing sheet to adhere to a metal foil or the like, but the concentration of the resin in the resin-containing sheet is preferably from 10 to 99% by volume, particularly preferably It is 10 to 70% by volume. By setting the impregnation rate of the resin composition within the above range, good adhesion and high strength can be obtained with good balance.

The resin composition forming the resin 3 may include at least one selected from the group consisting of thermosetting resin, photocurable resin, and thermoplastic resin. Depending on the application, one type may be used alone, or two or more types may be used in combination. use. Among these, from the viewpoint of physical properties of a cured product or a molded product, a thermosetting resin is preferably used, and an epoxy resin is more preferably used. When a thermosetting resin or a photocurable resin is used as the resin composition, the same thermosetting resin, photocurable resin, organic solvent, etc. as those exemplified for the fixing agent composition can be suitably used. In the invention, the resin composition and the fixing agent composition may be different from each other. As the thermoplastic resin, those shown below can be used.

(Thermoplastic resin)

Examples of the thermoplastic resin include acrylic acid, modified acrylic acid, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, and polybenzene. Ethylene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid, etc. Amidine, thermoplastic polyurethane, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polybutylene terephthalate, modified polyphenylene ether, polyfluorene (PSF), polyphenylene sulfide Ether (PPS), polyether fluorene (PES), polyether ether ketone, polyacrylate, polyether fluorene imine, polyamine fluorene imine, liquid crystal polymer, polyamine 6T, polyamine 9T, polytetramethylene Fluoroethyl Engineering plastics such as olefin, polyvinylidene fluoride, polyester fluorene, thermoplastic polyfluorene, olefin, styrene, polyester, urethane, fluorene, vinyl chloride Based thermoplastic elastomers. In the present invention, a resin composite may be used. For example, as the resin composite of a thermosetting resin and a thermoplastic resin, epoxy resin-PSF, epoxy resin-PPS, epoxy resin-PES, and the like can be used.

In the fixing agent composition and the resin composition related to the present invention, a coloring agent may be blended as other components.

As a colorant, a well-known conventionally represented by a color index, such as a color pigment or dye, can be used. Examples include Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122 , 136, 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 93 , 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1 , 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87 , 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 61, 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112 , 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, 37, 38, 41, 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, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42 ,, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, etc.

In addition, the anchoring agent composition and the resin composition related to the present invention may contain a defoaming agent if necessary. Leveling agent, thixotropy imparting agent. Conventional additives such as tackifiers, coupling agents, dispersants, and flame retardants.

As a defoamer. As the leveling agent, compounds such as mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amine, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester and the like can be used. Wait.

As thixotropy imparting agent. As the thickener, clay minerals such as kaolin, Smectite, Montmorillonite, bentonite, talc, mica, and zeolite, or amorphous inorganic particles, polyamine-based additives, and modified urea systems can be used. Additives, wax-based additives, etc.

As the coupling agent, for example, alkoxy has methoxy and ethyl Reactive functional groups include vinyl, methacryl, propylene, methacryl, epoxy, cyclic epoxy, hydrogen thio, amine, diamine, anhydride, urea Groups, sulfides, isocyanates, and the like, for example, vinylethoxysilane, vinyltrimethoxysilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethyl Vinyl silane compounds such as oxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (amino (Ethyl) γ-aminopropylmethyldimethoxysilane, amine-based silane compounds such as γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, Epoxy-based silane compounds such as β- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-hydrothiopropyl Hydrosulfide-based silane compounds such as trimethoxysilane, silane coupling agents such as phenylamine-based silane compounds such as N-phenyl-γ-aminopropyltrimethoxysilane, and isopropyl triisocyanate Lipidation Titanate, tetraoctylbis (di-tridecyl phosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, isopropyltris (dodecyl) benzenesulfonate Fluorenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphate) titanate, tetra (1,1-diallyloxymethyl) 1-butyl) bis (di-tridecyl) phosphate titanate, bis (dioctylpyrophosphate) ethenyl titanate, isopropyltrioctylfluorenyl titanate, isopropyl Dimethylpropenyl isostearylfluorenyl titanate, isopropyltristearyl methacrylfluorenyl titanate, isopropyltris (dioctyl phosphate) titanate, isopropyl Titanate-based coupling agents such as tricumenyl phenyl titanate, dicumenyl phenoxyacetate titanate, diisostearyl ethynyl titanate, etc., containing ethylenic unsaturation The transformation of zirconate Compounds, compounds containing neoalkoxyzirconate, neoalkoxytrinedecanoyl zirconate, neoalkoxytris (dodecyl) benzenesulfonyl zirconate, neoalkoxy Tris (dioctyl) phosphate zirconate, neoalkoxytris (dioctyl) pyrophosphate zirconate, neoalkoxytris (ethylene diamino) ethyl zirconate, neoalkane Oxytri (m-amino) phenyl zirconate, tetra (2,2-diallyloxymethyl) butyl, bis (di-tridecyl) phosphite zirconate, neopentyl (Diallyl) oxy, trinedecylfluorenyl zirconate, neopentyl (diallyl) oxy, tris (dodecyl) benzenesulfonylzirconate, neopentyl (di Allyl) oxy, tris (dioctyl) phosphate zirconate, neopentyl (diallyl) oxy, tris (dioctyl) pyrophosphate zirconate, neopentyl (diallyl) ) Oxy, tris (N-ethylenediamino) ethyl zirconate, neopentyl (diallyl) oxy, tris (m-amino) phenyl zirconate, neopentyl (diene Propyl) oxy, trimethacrylfluorenyl zirconate, neopentyl (diallyl) oxy, tripropenylfluorenyl zirconate, dinepentyl (diallyl) oxy, di-p-amino Benzamidine zirconate, Neopentyl (diallyl) oxy, bis (3-hydrothio) propionic acid zirconate, zirconium (IV) 2,2-bis (2-acetanolacetone (propanolato) methyl) butanoic acid Zirconate-based coupling agents such as butanolato, cyclic di [2,2- (bis-2-acetamylacetonemethyl) butanoic acid] pyrophosphate-O, O, diisobutyl (oil Amidino) Acetoacetyl aluminates, aluminate-based coupling agents such as alkyl acetoacetyl aluminum diisopropyl ester, and the like.

As the dispersant, a polymer dispersion such as a polycarboxylic acid type, a naphthalenesulfonic acid formaldehyde (formalin) condensation type, polyethylene glycol, a polycarboxylic acid partially alkyl ester type, a polyether type, or a polyalkylene polyamine type can be used Agents, low molecular weight dispersants such as alkylsulfonic acid, quaternary ammonium, higher alcohol alkylene oxide, polyol ester, and alkylpolyamine.

As the flame retardant, hydrated metal systems such as aluminum hydroxide and magnesium hydroxide, red tincture, ammonium rhenate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compounds, bromine compounds, chlorine compounds, and phosphonates can be used. Fluorene-containing polyols, fluorene-containing amines, melamine cyanurates, melamine compounds, triazine compounds, guanidine compounds, polysiloxane polymers, and the like.

The anchor agent composition and the resin composition according to the present invention may include, in addition to the above, inorganic fillers such as barium sulfate, silicon dioxide, and hydrotalcite, nylon powder, fluorine powder, and the like, as long as the object of the present invention is not hindered. Organic fillers, free radical trapping agents, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors, surface treatment agents, surfactants, lubricants, antistatic agents, pH Conditioners, antioxidants, dyes, pigments, fluorescent agents, etc.

[Storage Modulus]

In the present invention, the storage modulus of the fixing agent 2 must be higher than that of the resin 3. Here, the so-called storage modulus of the fixing agent 2 means that the fiber 1 is not included, and the formulation of only the components of the fixing agent composition is hardened by heat or light after film formation. Storage modulus of the film. Similarly, regarding the storage modulus of resin 3, if it is a curable resin, it also means the storage modulus of a cured film obtained by curing by heat or light after film formation; if it is a thermoplastic resin In this case, it means the storage modulus of the coating film obtained after the solvent is removed after the film formation. In addition, the so-called "storage modulus" is an index value of the hardness of a sample, and it is referred to as a dynamic viscoelasticity measurement. When a periodic load is applied to the sample and strain is detected), the storage modulus is a value calculated from the detected strain. The higher the value, the better the mechanical strength. In the present invention, as long as the storage modulus of the fixing agent 2 is higher than the storage modulus of the resin 3 at any temperature, the suitable range is that the storage modulus of the fixing agent 2 is 30 to 0.1. GPa, and preferably 20 to 0.5 GPa; the storage modulus of resin 3 is 10 to 0.001 GPa, and preferably 5 to 0.01 GPa. At any temperature, the storage modulus of the fixing agent 2 is more than the resin The storage modulus of 3 is preferably larger than 0.1GPa. In particular, it is preferable that the storage modulus of the fixing agent 2 is higher than the storage modulus of the resin 3 at any temperature in the range of 150 to 250 ° C; and more preferably: 150 to 250 ° C In the whole temperature range, the storage modulus of the fixing agent 2 is higher than that of the resin 3. Thereby, the resin-containing sheet of the present invention can be used even in a high-temperature region of 150 to 250 ° C. Since the use is widened, it is preferable.

[Glass transition temperature]

In the present invention, it is preferable that the glass transition temperature of the fixing agent 2 is higher than the glass transition temperature or softening temperature of the resin 3. Here, the so-called glass transition temperature of the anchoring agent 2 means that the fiber 1 is not included, and the formulation of only the components of the anchoring agent composition is hardened by heat or light after film formation. Film glass transition temperature. Similarly, regarding the glass transition temperature or softening temperature of resin 3, in the case of a hardening resin, it also means the glass transition temperature of a hardened film obtained by hardening by heat or light after film formation; if it is In the case of thermoplastic resins, it means Softening temperature of the coating film obtained after removing the solvent after the film. The "glass transition temperature" is calculated from the ratio (E "/ E ') of the storage modulus (E') and the loss modulus (E") obtained in the aforementioned dynamic viscoelasticity measurement. The temperature at which the value (the loss is directly connected) is the maximum value. The higher the temperature, the more excellent the heat resistance is. In the present invention, the upper limit of the glass transition temperature is not particularly limited, and the suitable range is that the glass transition temperature of the fixing agent 2 is 130 ° C or higher, more preferably 140 ° C or higher, and particularly preferably 250 ° C or higher. When the glass transition temperature of the fixing agent 2 is higher, it is preferable because the storage modulus of the resin-containing sheet of the present invention becomes higher.

On the other hand, the glass transition temperature or softening temperature of the resin 3 is 70 ° C or higher, and more preferably 80 ° C or higher. The glass transition temperature of the fixing agent 2 is preferably 5 ° C or more higher than the glass transition temperature or softening temperature of the resin 3.

[Manufacture of resin-containing sheet]

The resin-containing sheet of the present invention can be obtained by treating the fiber base material 11 with a fixing agent composition and fixing the fibers 1 to each other, and then impregnating the resin composition with the fixed fiber base material 11. In the resin-containing sheet of the present invention, for example, a state in which fibers are arranged on a coated object such as a carrier film can be used to sequentially coat and impregnate a fixing agent composition and a resin composition, and volatilize to dry and fix the resin composition. The organic solvent contained in the agent composition and the resin composition can be produced as a dry film, and a cover film can be further bonded thereon if desired. In this case, as long as the resin composition does not hinder the fixing performance of the anchor composition to the fiber, the coating of the resin composition The cloth manufacturing process can be before or after the fixing agent is dried.

In this case, the anchoring agent composition and the resin composition of the present invention may be prepared by mixing, dispersing, and diluting each component and adjusting the viscosity to a coating method suitable for coating. As described above, the fixing agent composition may saturate the fibrous base material 11 and fix the fibers 1 to each other; and the resin composition may be a surface capable of at least one of the fibrous base materials 11. (Especially on both sides of the fibrous base material 11) may be adhered to a metal foil or the like.

As the object to be coated, a carrier film for a dry film is preferred, but it can also be directly applied to the surface of a metal foil or the surface of a wiring board on which a circuit has been formed. As specific examples of the coating method, for example, a dropping method using a dripper, a dip coating method, a rod coating method, a spin coating method, a curtain coating method, a spray coating method, a roll coating method, or a slit coating method are mentioned. Various coating methods such as cloth method, doctor blade coating method, die lip coating method, notch wheel coating method, film coating method, or screen printing, liquid jet printing, inkjet printing, letterpress printing, gravure printing , Lithography and other printing methods.

The carrier film and the cover film can be arbitrarily used as materials known as dry films. Examples include polyethylene films and polypropylene films. The carrier film and the cover film may use the same film material or different film materials. Regarding the cover film, the adhesiveness with the resin 3 is preferably smaller than the carrier film.

By making the resin-containing sheet of the present invention adhere to the substrate, a structure can be obtained. Examples of the substrate include a metal foil substrate, a circuit substrate (a wiring board on which a circuit is formed), and the like. By making the resin-containing sheet of the present invention The resin insulation layer can be formed by heat-adhering to the surface of the substrate, and by repeating the operation, a plurality of separate layers of the metal foil layer and the resin insulation layer can also be laminated. In addition, when the resin-containing sheet is manufactured on a carrier film, the resin-containing sheet may be laminated with each other, or the resin-containing sheet may be laminated with each other when the resin-containing sheet is adhered to a metal foil or the like.

When the resin-containing sheet of the present invention is used to produce a structure, when the fixing agent composition and the resin composition are a combination of a thermosetting resin or a photocurable resin, only heat-curing method is used and only active energy is used. A structure can be produced by a method of ray irradiation, a method of heating and hardening after irradiation with active energy rays, or a method of irradiating with active energy rays after heat curing. When a dry film is used, the cover film is peeled off when the cover film is provided, the resin-containing sheet is heat-adhered to the substrate surface, and then the carrier film is peeled and hardened by the above-mentioned hardening method to produce a structure. In addition, when the thermosetting resin is used together as the fixing agent composition and the resin composition, both the heat curing process of fixing the fibers to each other and impregnating the resin may be performed at the same time. The heating temperature during heating may be a range in which the fibers or the fixing agent contained in the target substrate do not decompose due to high heat. The lower limit and the upper limit are not particularly limited. The active energy ray irradiation is performed. The exposure amount at this time is not limited as long as there is no uncured portion due to an excessively low exposure amount.

When the resin-containing sheet of the present invention is produced, when the resin composition is a thermoplastic resin, a pellet-shaped or sheet-shaped thermoplastic resin may be heated, or heated or pressed. in Here, in order to impregnate the thermoplastic resin into the fibrous base material fixed by the fixing agent, it is not necessary to press using a device, but the thermoplastic resin can be impregnated into the fiber by pressing. It becomes easier inside the substrate. When the pressure is applied, the upper limit of the pressure is not particularly limited as long as the shape of the intended resin-containing sheet is not impaired. By heat-adhering the resin-containing sheet to the substrate surface, a structure can be formed. When a structure is formed using a dry film, it can be produced in the same manner as described above.

Among the above, as a device used during drying, heat curing, or heating and pressing, for example, a hot-air circulation drying furnace, an IR furnace, a heating plate, a convection heating oven, a heating and pressing roller, a press, etc. . Examples of light sources for active energy ray irradiation include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halogen lamps. In addition, a laser ray or the like may be used as the active energy ray.

The thickness of the fibrous base material of the resin sheet-containing constituent member of the present invention, the fibers that are fixed to each other by a fixing agent (hereinafter also referred to as "intermediate"), and the thickness of the dry film are not particularly limited, and can be adapted according to the purpose. It is appropriately selected, but especially for the intermediate, as long as the fibers can be fixed to each other by a fixing agent, the thickness is preferably: the same level as the thickness of the fiber substrate, or not more than the fiber substrate The film thickness is about 2 times the thickness. Specifically, it is preferably within a range of 1 to 1.5 times the thickness of the fiber substrate. When the thickness of the intermediate is more than twice the thickness of the fiber substrate, it is not suitable because the physical properties of the fixing agent itself will be affected.

The structure obtained by forming the resin-containing sheet of the present invention on the surface of a substrate and curing or molding it can be used as a core material for a wiring board. It can also be used as an interlayer insulation material for wiring boards by performing an etching process or the like. In addition, when a resin-containing sheet is formed on the surface of a wiring board on which a circuit has been formed, and it is patterned, hardened, or molded so that it becomes a structure only by covering the circuit wiring, it can also be used as a wiring board. Use the outer layer of solder resist.

The resin-containing sheet of the present invention having the structure described above can be applied to wiring boards for electronic devices and the like. For example, it can be suitably used for interlayer insulation materials, solder resists, and core materials for wiring boards. The desired effect of the present invention. In addition, for example, the fibers are fixed to each other with a fixing agent composition, and the resin is impregnated and dried to form a resin insulation layer in a semi-hardened state (B-stage), and the resin insulation layer and the metal foil are laminated. Pressing can also make multilayer boards.

[Example]

Hereinafter, the present invention will be described in more detail with examples and comparative examples, but the present invention is not limited by these examples and comparative examples. In addition, the compounding amount in the following table is all expressed in mass parts.

[Synthesis of Polyamic Acid Varnish 1]

Put a dehydrated N-methyl-2-pyrrolidone (NMP) solvent (manufactured by Wako Pure Chemical Industries, Ltd.) into a three-necked flask with a stirrer substituted with nitrogen, and mix it with a 1: 1 molar ratio of 4 , 4'-Diaminodiphenyl ether (ODA) (manufactured by Wako Pure Chemical Industries, Ltd.) and 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) (Wako Pure Chemical Industries, Ltd.) (Manufactured), and stirred at room temperature for more than 16 hours to obtain a solid resin content Polyamic acid varnish 1 having a ratio of 7.5% by mass.

[Synthesis of Polyamic Acid Varnish 2]

In a nitrogen-replaced three-necked flask equipped with a stirrer, a dehydrated N-methyl-2-pyrrolidone (NMP) solvent (manufactured by Wako Pure Chemical Industries, Ltd.) was placed, and p was prepared at a molar ratio of 1: 1. -Phenylenediamine (PDA) (manufactured by Wako Pure Chemical Industries, Ltd.) and 3,3 ', 4,4'-biphenyltetracarboxylic anhydride (BPDA) (manufactured by Wako Pure Chemical Industries Ltd.) at room temperature After stirring for 16 hours or more, a polyamic acid varnish 2 having a resin solid content ratio of 7.5% by mass was obtained.

[Preparation of anchoring agent composition or resin composition]

The following Table 1 shows the blending contents of Compositions 1 to 4 which are used as a fixing agent composition or a resin composition. Each composition was prepared according to the description of the composition 1-4 in the following Table 1. In the case of a plurality of components of the composition 1, after each component is prepared, it is stirred and prepared using a rotation and revolution mixer.

[Preparation of test pieces for evaluation of storage modulus of resin or resin]

Each of the compositions 1 to 4 was applied on a copper foil having a thickness of 18 μm using an applicator to obtain a coating film.

The composition 1 was dried in an air condition using a hot-air circulation drying furnace at 80 ° C for 30 minutes, and then heated at 150 ° C for 60 minutes to obtain an epoxy resin cured product. When the copper foil was removed, the thickness was 50 μm. Use this hardened material to make a storage mold with a width of 5mm and a length of 50mm Number of test pieces for evaluation.

About composition 2, after coating, it was dried in a hot-air circulation drying oven at 80 ° C for 30 minutes under atmospheric conditions, and then heated at 250 ° C for 60 minutes under nitrogen conditions (100ml / min.) To obtain ammonium imine. Compound. When the copper foil was removed, the thickness was 50 μm. Thereafter, a test piece for evaluation was produced in the same manner as described above.

The composition 3 was prepared in the same manner as the composition 2 except that the heating operation was performed under nitrogen conditions at 300 ° C. and 60 minutes.

Regarding Composition 4, high-density polyethylene particles (specific gravity: 0.95) were put into a press in an appropriate amount, heated and pressurized at 140 ° C, 3 MPa, and 3 minutes, and then cooled to room temperature to obtain a molded body. When individualized into pieces, the thickness is 50 μm. Thereafter, a test piece for evaluation was produced in the same manner as described above.

[Production of test pieces for evaluation of storage modulus of resin-containing sheets and sheets]

The following Tables 2 and 3 show the structures of the resin-containing sheets and the sheets of the respective examples and comparative examples.

(Production of the intermediate of Example 1-A)

Regarding Example 1-A in Table 2 below, a glass cloth (type 1035 (IPC specification), thickness 30 μm) was used as a fiber substrate, and the above-mentioned composition 1 (viscosity 0.0005 Pa · s) was impregnated in this The fiber substrate was dried in a hot-air circulating drying furnace at 80 ° C for 30 minutes under atmospheric conditions, and then heated and cured at 150 ° C for 60 minutes to obtain a glass cloth and a fixing agent (ring An intermediate composed of a cured product of an oxygen resin composition).

(Production of the intermediate of Example 2-A)

Regarding Example 2-A in Table 2 below, the composition 2 (viscosity 0.001 Pa · s) was impregnated in the same glass cloth as in Example 1-A, and then heated in a hot-air circulation drying furnace at 80 ° C, After drying under atmospheric conditions for 30 minutes, it was heated at 250 ° C. for 60 minutes and then imidized to obtain an intermediate composed of a glass cloth and a fixing agent (polyimide).

(Production of the intermediate of Example 3-A)

Regarding Example 3-A in Table 2 below, the composition 3 (viscosity 0.001 Pa · s) was impregnated in the same glass cloth as in Example 1-A, and then heated in a hot-air circulation type drying furnace at 80 ° C, After drying under atmospheric conditions for 30 minutes, it was heated at 300 ° C. for 60 minutes and then imidized to obtain an intermediate composed of a glass cloth and a fixing agent (polyimide).

(Production of intermediate of Comparative Example 4-A)

In the same manner as in Example 1-A, the above-mentioned composition 1 was used to prepare an intermediate composed of a glass cloth and a fixing agent (a cured product of an epoxy resin composition).

The thickness of each intermediate of Examples 1-A to 3-A and Comparative Example 4-A was 33 to 35 μm. It can be known from the thickness of the glass cloth that the increase in thickness is only 3 to 5 μm.

(Production of the intermediate of Example 1-B)

Regarding Example 1-B in Table 3 below, except that polyaramide (Nomex 410, thickness 50 μm) was used as the fiber, the same process as in the production of the intermediate of Example 1-A was performed to An intermediate made of polyaramide and a fixing agent (hardened product of epoxy resin composition) is produced.

(Production of the intermediate of Example 2-B)

Regarding Example 2-B in Table 3 below, except that the same polyaramide woven fabric as that used in Example 1-B was used as the fiber, the same process as in the production of the intermediate of Example 2-A was performed. To produce an intermediate composed of polyaramide and a fixing agent (polyimide).

(Production of Intermediate of Example 3-B)

Regarding Example 3-B in Table 3 below, except that the same polyarylamide nonwoven fabric as that used in Example 1-B was used as the fiber, the same process as in the production of the intermediate of Example 3-A was performed. To produce an intermediate composed of polyaramide and a fixing agent (polyimide).

(Comparative Example 4-B Production of Intermediate)

In the same manner as in Example 1-B, using the composition 1 described above, an intermediate composed of a glass cloth and a fixing agent (a cured product of an epoxy resin composition) was prepared.

Examples 1-B ~ 3-B and Comparative Examples 4-B The thickness is 53 to 56 μm. It can be known from the thickness of the polyarylamide nonwoven fabric that the increase in thickness is only 3 to 6 μm.

(Production of resin-containing sheets and even sheets of each example and comparative example)

Regarding Example 1-A and Example 1-B, the above composition 4 was put into a press and melted at 140 ° C, and then impregnated into each of the intermediates obtained above at 140 ° C, 3 MPa, 3 After heating and pressing for one minute, and cooling to room temperature, a resin (high-density polyethylene resin) impregnated with glass cloth or aramid nonwoven cloth fixed with a fixing agent (epoxy) was produced. Contains resin flakes.

Regarding Example 2-A, Example 2-B, Example 3-A, and Example 3-B, an appropriate amount of the above-mentioned composition 1 was applied so that each of the intermediates obtained above could be cast to the entire fiber. And impregnated with the same conditions as described above for the preparation of the test piece for the evaluation of the fixing agent or the resin, and heating and curing the test piece under the same conditions, thereby producing a resin (hardened epoxy resin) impregnated with the fixing agent (polymer Resin-containing sheet made of glass cloth or polyaramide non-woven cloth fixed by imimine).

The thickness of each resin-containing sheet of Examples 1-A to 3-A and Examples 1-B to 3-B is 5 to 10 μm thicker than the thickness of the intermediate sheet. Thereafter, for each resin-containing sheet, a test piece for evaluation was produced under the same conditions as described above.

With regard to Comparative Examples 1-A and Comparative Example 1-B, an appropriate amount of the above-mentioned composition 1 was applied so that the glass cloth or the polyaramide nonwoven fabric could be cast to the entire fiber, and impregnated with the fixing agent. Or the test piece for resin evaluation is produced by heating and curing under the same conditions. A sheet obtained by impregnating a resin (epoxy resin cured product) with a glass cloth or a polyaramide nonwoven fabric that does not contain a fixing agent.

Regarding Comparative Example 2-A and Comparative Example 2-B, the composition 2 was applied to a glass cloth or a polyaramide nonwoven fabric in the same manner as in Comparative Example 1-A, and impregnated with a hot-air circulation drying furnace. After drying under atmospheric conditions at 80 ° C for 30 minutes, the glass cloth was made by impregnating the resin (polyimide) with an imidization agent by heating at 250 ° C for 60 minutes under atmospheric conditions. Or a thin sheet made of polyaramide.

Regarding Comparative Example 3-A and Comparative Example 3-B, the above-mentioned composition 4 was put into a press and melted at 140 ° C, and then impregnated in a glass cloth or a polyimide nonwoven fabric at 140 ° C, 3 MPa, After heating and pressing for 3 minutes, and cooling to room temperature, a sheet obtained by impregnating a resin (high-density polyethylene resin) with a glass cloth or a polyaramide nonwoven fabric not containing a fixing agent was produced.

Regarding Comparative Example 4-A and Comparative Example 4-B, except that the glass cloth or the polyaramide nonwoven fabric in Comparative Example 2-A and Comparative Example 2-B was changed to use the fixing having the composition 1 described above. Except for the intermediate of the agent, a resin-containing sheet was prepared in the same manner as in Comparative Examples 2-A and 2-B.

Thereafter, test pieces for evaluation were produced for each sheet in the same manner as described above.

The resin content and concentration are as shown in the following Tables 2 and 3, and they are about the same as those of Examples 1-A to 3-A and Comparative Examples 1-A to 4-A. Also, about Example 1-B ~ 3-B and Comparative Examples 1-B ~ 4-B also have the same degree. Here, the resin amount concentration is based on: fixation dose = {1- (volume of fiber substrate / volume of intermediate)} × 100 [vol.%], Resin amount = {1- (middle The volume of the body / the volume of the resin-containing sheet or sheet)} × 100 [vol%] (the volume is obtained by conversion based on mass and specific gravity).

[Measurement of storage modulus, etc.]

Using a test piece for evaluation such as a storage modulus of a fixing agent or a resin, a DMA viscoelasticity measuring device (DMA7100 manufactured by Hitachi High-Tech Science) was used to measure a frequency of 1 Hz, a minimum tension, and a minimum compression force. 200 mN, strain amplitude of 10 μm, heating rate of 5 ° C / min, and measurement of viscoelasticity under atmospheric conditions, and storage modulus of 50 ° C, 150 ° C and 250 ° C, and glass transition temperature or softening temperature were obtained. The results are shown in Table 1 below.

＊ 1: jER828, Mitsubishi Chemical Corporation

＊ 2: 2-Ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd.

＊ 3: Wako Pure Chemical Industries, Ltd.

＊ 4: Specific gravity 0.95

[Evaluation of storage modulus of resin-containing sheet or sheet]

For resin-containing sheets or test sheets for sheet evaluation, the test pieces are fixed in such a way that the direction of the fiber of the glass cloth or polyaramide nonwoven fabric in the sheet becomes the stretching direction of the device, and the minimum tension and The compressive force was set to 50 mN, and viscoelasticity was measured in the same manner as described above to obtain storage modulus of 50 ° C, 150 ° C, and 250 ° C. Here, the reason why the measurement is performed in the bias direction is to exclude the influence of the modulus of the fiber base material as much as possible in order to investigate the influence of the increase in modulus caused by the fixing effect. For each Example, compare it with the sheet | seat of the comparative example to which the fixing agent was not adhered. At this time, when the value of the storage modulus E [GPa] is large, it is marked as ○, and the value of the storage modulus E [GPa] Hours are marked with ×.

To explain in detail, the resin-containing sheet of Example 1-A has a storage modulus at 50 ° C, 150 ° C, and 250 ° C compared to the sheet of Comparative Example 3-A without a fixing agent. The values of E [GPa] are all large, so they are marked as "○".

Compared with the sheet of Comparative Example 3-B in which no fixing agent was used, the value of the storage modulus E [GPa] of Example 1-B was also large, so it was marked as "○".

Compared with the sheet of Comparative Examples 1-A and 1-B without a fixing agent, the storage modulus E of the resin-containing sheet of Examples 2-A, 2-B, 3-A, and 3-B was also compared. The value of [GPa] is large, so the mark is "○".

On the other hand, the resin-containing sheet of Comparative Example 4-A had a storage modulus E at a temperature of 50 ° C, 150 ° C, or 250 ° C compared to the sheet of Comparative Example 2-A without a fixing agent. The value of [GPa] is small, so it is marked as "×".

The resin-containing sheet of Comparative Example 4-B was marked as "×" compared to the sheet of Comparative Example 2-B in which no fixing agent was used.

The results are shown in Tables 2 and 3 below.

For reference, when only the glass cloth is used for the above-mentioned measurement, the woven fiber is disentangled at the beginning of the measurement due to the stretching in the oblique direction, so the value of the storage modulus cannot be obtained.

[Production of test piece for adhesion evaluation]

Except that a glass cloth or a polyaramide nonwoven fabric as a fibrous base material is arranged on a carrier film, the same operations as described above are performed to apply and impregnate a fixing agent composition to prepare each intermediate. Thereafter, a resin composition is formed or coated on the surface of the dried fixing agent, and the cover film is bonded after drying to obtain a dry film. A surface untreated copper foil with a thickness of 18 μm was laminated to both sides of the dry film (the carrier film and the cover film were peeled off during adhesion), and a vacuum pressing machine was used under the conditions of pressure of 1 MPa and heating. 1-A and 1-B: 150 ° C x 10 minutes; Examples 2-A and 2-B, Comparative Examples 4-A and 4-B: 250 ° C x 60 minutes; Examples 3-A and 3-B: It was molded at 300 ° C. × 60 minutes to prepare a test piece for evaluation of adhesion between the resin layer and the copper foil. In addition, about Comparative Examples 1-A to 3-A and Comparative Examples 1-B to 3-B, except that the uncoated and impregnated fixing agent composition was used, a dry film was produced in the same manner, and pressure was applied using a vacuum press. In the same temperature conditions as the sheet preparations of Comparative Examples 1-A to 3-A and Comparative Examples 1-B to 3-B, test pieces for adhesion evaluation were produced.

[Evaluation of adhesion]

Using a test piece for adhesion evaluation, the peel strength of the resin layer and the surface untreated copper foil to peel them off at the interface was measured at a peel angle of 90 ° and a peel speed of 50 mm / min. When it is 0.5 kN / m or more, it is marked as ○, and when it is less than 0.5 kN / m, it is marked as x. The results are shown in Tables 2 and 3 below. At high peel strength, the adhesiveness following the unevenness is excellent, and it can be said that the adhesiveness to the copper foil is excellent.

As shown in Tables 2 and 3 above, the storage modulus of the fixing agents of Examples 1-A to 3-A and Examples 1-B to 3-B are all compared to the storage modulus of the resin. On the other hand, in Comparative Examples 4-A and 4-B, the storage modulus of the fixing agent is small compared to the storage modulus of the resin. In Comparative Examples 1-A to 3-A and 1-B to 3-B, only resin was used, and no fixing agent was used.

As shown in Tables 2 and 3 above, examples in which the storage modulus of the fixing agent is higher than the storage modulus of the resin to fix glass cloth or polyimide nonwoven fabric, and further impregnate the resin As compared with the sheet of the comparative example which was impregnated with resin only, the resin-containing sheet of Example 2 shows that the resin-containing sheet of the example is excellent in adhesiveness and has a large storage modulus.

For example, when comparing Example 1-A with Comparative Example 3-A, it can be clearly seen that the fibers of the glass cloth are fixed to each other by fixing the composition, and the resin composition is impregnated into the fiber substrate. The resin-containing sheet of the example has a storage modulus of the resin-containing sheet of the example at any temperature as compared to Comparative Example 3-A in which the fibers of the glass cloth are not fixed to each other by the fixing composition. Is high, it can be known that the mechanical strength is high.

In particular, the resin-containing sheets of Examples 2-A, 3-A and Examples 2-B, 3-B have storage modulus at 250 ° C of more than 1 GPa, and it can be seen that the mechanical strength at high temperatures is also excellent. On the other hand, the storage modulus of the anchoring agent is comparative example 4-A and comparative example 4-B, which are lower than the storage modulus of the resin. The storage modulus of the resin-containing sheet is low, and the adhesion is also poor. .

From the above, it can be confirmed that by using a resin having a fixing agent that fixes the fibers in the fibrous substrate to each other and a resin that contacts the fixed fiber, the storage modulus of the fixing agent is higher than that of the resin. The resin-containing sheet having a high number can achieve excellent mechanical strength, modulus, and adhesion. Such a resin-containing sheet of the present invention can be applied to a wiring board for an electronic device and the like, and can be suitably used, for example, as an interlayer insulating material, a solder resist, a core material, or the like for a wiring board.

Claims (7)

A resin-containing sheet comprising: a fiber substrate; a fixing agent for fixing fibers in the fiber substrate to each other; a resin contacting the fiber substrate and the fixing agent; and a storage modulus of the fixing agent It is higher than the storage modulus of the foregoing resin, and is characterized in that the storage modulus of the foregoing fixing agent is 30 to 0.1 GPa, the storage modulus of the foregoing resin is 10 to 0.001 GPa, and the storage of the fixing agent at 50 ° C is The modulus is 0.1 ~ 1.2GPa (but not including 1.2GPa) higher than the storage modulus of the resin. The resin-containing sheet according to claim 1, wherein the glass transition temperature of the fixing agent is higher than the glass transition temperature or softening temperature of the resin. The resin-containing sheet according to claim 1, which is obtained by fixing the fibers of the fibrous base material to each other with a fixing agent composition, and then impregnating the fixed fiber base material with the resin composition. The resin-containing sheet according to claim 3, wherein the viscosity of the anchoring agent composition is 1 Pa · s or less. The resin-containing sheet according to claim 1, wherein the fiber substrate comprises a woven fabric or a non-woven fabric. A structure characterized in that the resin-containing sheet of claim 1 is obtained by closely adhering to a substrate. A wiring board characterized by having the structure of claim 6.