JP5363841B2 - Epoxy resin composition, prepreg, cured body, sheet-like molded body, laminate and multilayer laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such a resin composition that, when the surface of its cured product is roughening-treated, the surface roughness is slight after the roughening treatment, and when a metallizing layer is formed on the surface of its cured product, the adhesiveness between the cured product and the metallizing layer is improved, and to provide a prepreg, a cured product, a sheet-like molded form, a laminated board and a multi-layer laminated board, each using the above resin composition. <P>SOLUTION: The resin composition, an epoxy-based one, comprises an epoxy-based resin (a), a curing agent (b) for the epoxy-based resin, silica (c) treated with either one or more of aminosilane and epoxysilane and having an average particle size of 5 &mu;m or smaller, and a nonionic surfactant (d). In this resin composition, the amounts of the silica (c) and the nonionic surfactant (d) are 25-400 pts.wt. and 0.1-10 pt.wt., based on 100 pts.wt. of the mixture (a+b) of the epoxy-based resin (a) and the curing agent (b), respectively. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an epoxy resin composition, a prepreg, a cured body, a sheet-like molded body, a laminate and a multilayer laminate, and more specifically, for use in applications such as a substrate on which a copper plating layer is formed. The present invention relates to an epoxy resin composition, a prepreg using the resin composition, a cured body, a sheet-like molded body, a laminate, and a multilayer laminate.

  Conventionally, for example, as a resin or resin composition used in a semiconductor device or the like, a resin composition containing an epoxy resin containing a filler treated with imidazole silane has been used. Various attempts to improve various physical properties have been made and proposed (see, for example, Patent Documents 1 to 4).

Patent Document 1 discloses a resin composition containing a filler treated with a specific imidazole silane or a mixture of specific imidazole silanes as a sealing resin for a semiconductor device. In this resin composition, an imidazole group present on the surface of the filler acts as a curing catalyst and a reaction starting point. Therefore, chemical bonds are likely to occur, and curing the resin composition can increase the strength of the cured resin and is particularly useful when adhesion is required.
Patent Document 2 discloses an epoxy resin composition containing imidazole silane having an alkoxysilyl group or dimethylaminosilane having an alkoxysilyl group. This epoxy resin composition is said to be excellent in curability, adhesion, and storage stability.
Furthermore, Patent Document 3 discloses an imidazole silane (D) in which Si atoms and N atoms are not directly bonded in a resin composition containing an epoxy resin (A), a phenol resin (B), and an inorganic filler (C). ) Is contained in an amount of 0.01 to 2.0 parts by weight. This epoxy resin composition is excellent in adhesiveness to a semiconductor chip, does not peel even after IR reflow, and is also excellent in moisture resistance.

  In addition, the present inventors also disclosed a resin composition containing, in Patent Document 4, an epoxy resin, a curing agent for the epoxy resin, and silica having an average particle diameter of 5 μm or less treated with imidazole silane. The resin composition described in Patent Document 4 has a small surface roughness after the roughening treatment (etching) during wiring formation, excellent copper plating adhesion, and excellent fine wiring compatibility.

  However, in recent years, as the L / S of copper wiring is further reduced, a resin composition that constitutes an insulating material is required to have a lower linear expansion coefficient. And in order to make a linear expansion coefficient low, generally increasing the content rate of inorganic fillers (or fillers), such as a silica, is carried out, but inorganic fillers (or fillers), such as a silica, are carried out. When the ratio is increased, there is a problem that the surface roughness after the roughening treatment increases. Further, when the silica content is too high, there is a problem that the plating peel strength of the copper plating is lowered.

  The object of the present invention is to take into account the current state of the prior art described above, and when the surface of the cured product of the resin composition is roughened, the surface roughness after the roughening treatment is small, and the resin composition is cured. When a plated layer is formed on the surface of a product, a resin composition having improved adhesion between the cured product and the plated layer or adhesion, a prepreg using the resin composition, a cured product, and a sheet-like molded product It is in providing a laminated board and a multilayer laminated board.

  As a result of intensive studies to solve the above problems, the present inventors have found that epoxy resin, curing agent, silica having a specific diameter treated with imidazole silane, and nonionic surfactant are contained in a specific ratio. The composition has a good dispersion state of silica, and when the surface of the cured product is roughened, the surface roughness after the roughening treatment is suitable, and the above-described problems are achieved. . Based on these findings, the present invention has been further studied and completed.

  That is, according to the first invention of the present invention, the epoxy resin (a), the epoxy resin curing agent (b), and any one or more of imidazole silane, amino silane, and epoxy silane are processed, and the average A resin composition containing silica (c) having a particle size of 5 μm or less and a nonionic surfactant (d), and a mixture of an epoxy resin (a) and a curing agent for epoxy resin (b) (A + b) An epoxy resin composition comprising silica (c) in an amount of 25 to 400 parts by weight and nonionic surfactant (d) in a proportion of 0.1 to 10 parts by weight with respect to 100 parts by weight of (a + b). Things are provided.

According to a second invention of the present invention, in the first invention, the nonionic surfactant (d) is selected from the group consisting of an ester surfactant, an ether surfactant, and an ester / ether surfactant. An epoxy resin composition is provided that is at least one selected.
According to the third invention of the present invention, in the first or second invention, the silica (c) treated with any one or more of imidazole silane, amino silane, and epoxy silane is 100 parts by weight of silica, An epoxy resin composition characterized in that the treatment amount with imidazole silane, aminosilane or epoxysilane is 0.1 to 5 parts by weight.
Furthermore, according to the fourth invention of the present invention, there is provided an epoxy resin composition characterized in that, in any one of the first to third inventions, the imidazole silane has no hydroxyl group in the molecule.

According to the fifth invention of the present invention, in any one of the first to fourth inventions, the epoxy resin (a) has an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, and an adamantane skeleton. An epoxy resin composition comprising 5% by mass or more of at least one selected from the group consisting of an epoxy resin, an epoxy resin having a triazine skeleton, and an epoxy resin having a biphenyl skeleton with respect to the total amount of the epoxy resin Is provided.
Furthermore, according to the sixth invention of the present invention, in any one of the first to fifth inventions, the epoxy resin curing agent (b) comprises a curing agent having a biphenyl skeleton, an active ester curing agent, a benzoxazine structure. 5 mass% or more of at least one selected from the group consisting of a curing agent containing an aminotriazine skeleton and a curing agent having a naphthalene skeleton with respect to the total amount of the epoxy resin curing agent. An epoxy resin composition is provided.

According to a seventh aspect of the present invention, there is provided an epoxy resin composition characterized in that in any one of the first to sixth aspects, the silica (c) has an average particle size of 1 μm or less. .
According to the eighth invention of the present invention, in any one of the first to seventh inventions, 100 parts by weight of the mixture (a + b) of the epoxy resin (a) and the epoxy resin curing agent (b) is used. On the other hand, an epoxy resin composition characterized by further containing an organically modified layered silicate (e) having an average particle diameter of 500 nm or less in a proportion of 2 parts by weight or less is provided.
Furthermore, according to the ninth invention of the present invention, in any one of the first to eighth inventions, the maleimide compound (f) is further contained in an amount of 2 to 45% by mass based on the total amount of the resin composition. An epoxy resin composition is provided.

On the other hand, according to the tenth aspect of the present invention, there is provided a prepreg obtained by impregnating a porous substrate with the epoxy resin composition according to any one of the first to ninth aspects.
Further, according to the eleventh invention of the present invention, the epoxy resin composition according to any one of the first to ninth inventions or the resin cured product obtained by heat-curing the prepreg according to the tenth invention is roughened. Provided is a cured body that has been subjected to a treatment and has a surface roughness Ra of 0.2 μm or less and a surface roughness Rz of 2.0 μm or less.
Furthermore, according to a twelfth aspect of the present invention, there is provided the cured body according to the eleventh aspect, wherein a swelling treatment is performed before the resin cured product is roughened.

According to the thirteenth aspect of the present invention, there is provided the epoxy resin composition according to any one of the first to ninth aspects, the prepreg according to the tenth aspect, or the cured body according to the eleventh or twelfth aspect. A sheet-like molded body characterized by being used is provided.
Furthermore, according to the fourteenth aspect of the present invention, the laminate is characterized in that a metal layer and / or an adhesive layer having adhesiveness is formed on at least one surface of the sheet-like molded body according to the thirteenth aspect. A board is provided.

According to a fifteenth aspect of the present invention, there is provided the laminated board according to the fourteenth aspect, wherein the metal layer is formed as a circuit.
Furthermore, according to the sixteenth aspect of the present invention, there is provided a multilayer laminated board characterized by laminating at least one kind of laminated board selected from the laminated boards according to the fourteenth or fifteenth invention.

  The epoxy resin composition of the present invention is treated with an epoxy resin (a), a curing agent for epoxy resin (b), and any one or more of imidazole silane, aminosilane, and epoxy silane, and the average particle size is A resin composition containing silica (c) having a size of 5 μm or less and a nonionic surfactant (d), and a mixture (a + b) of an epoxy resin (a) and an epoxy resin curing agent (b) Since the silica (c) is contained in an amount of 25 to 400 parts by weight and the nonionic surfactant (d) is contained in a proportion of 0.1 to 10 parts by weight with respect to 100 parts by weight, particularly a specific silica Since the resin composition contains a specific amount, the surface of the cured product can be reduced by removing the silica easily without etching much resin by roughening the resin composition after heat treatment. This Can. Moreover, since the pores on the surface of the cured product (cured body) are those from which silica having an average particle diameter of 5 μm or less is detached, the average diameter of the holes is about 5 μm or less. Further, silica treated with imidazole silane, aminosilane, or epoxy silane tends to agglomerate and the surface roughness tends to increase as the average particle size is 1 μm or less and the content increases, but nonionic surfactants ( By containing a specific amount of d), it is possible to maintain good dispersibility even when the content of silica treated with imidazole silane, aminosilane or epoxysilane having an average particle diameter of 1 μm or less is large. Therefore, it is possible to obtain a cured body excellent in copper plating adhesiveness in which the resin portion is smooth and the fine irregularities from which silica having an average particle diameter of 5 μm or less is detached are formed.

In the present invention, when a roughening treatment is carried out after the resin composition is heat-cured, a plurality of fine holes from which silica has been detached are formed on the surface of the cured product. Therefore, for example, when a metal plating layer such as copper is formed on the surface of the cured product, the metal plating layer reaches the inside of the plurality of holes formed on the surface. Therefore, the adhesion between the cured product and the metal plating can be enhanced by the physical anchor effect.
In addition, when the average particle diameter of silica is 1 μm or less, the resin composition is heated and cured, and further subjected to, for example, swelling or roughening treatment, the silica treated with imidazole silane, aminosilane or epoxy silane It can be desorbed more easily. Further, as the average particle diameter of silica is smaller, silica is more easily detached and the formed pores are finer. Thereby, a fine uneven surface is formed on the surface of the cured product. Therefore, when a metal plating layer such as copper is formed on the surface of the cured product, the adhesion between the cured product and the metal plating can be further enhanced.
Furthermore, when the organic layered silicate (e) is further contained in a proportion of 2 parts by weight or less with respect to 100 parts by weight of the mixture (a + b) comprising the epoxy resin (a) and the epoxy resin curing agent (b). The organic layered silicate (e) is dispersed around the silica (c) treated with imidazole silane, aminosilane or epoxy silane. Therefore, after curing the resin composition, for example, by performing swelling and roughening treatment, silica (c) treated with imidazole silane, aminosilane or epoxy silane present on the surface of the cured product can be more easily obtained. Can be desorbed. Therefore, a fine and uniform uneven surface can be formed on the surface of the cured product. Therefore, when the metal plating layer etc., such as copper, are formed in the surface of hardened | cured material, the adhesiveness of a hardening body and metal plating can be improved, for example.
In Patent Document 4, the organically modified layered silicate (e) is defined as a ratio of 0.1 to 50 parts by weight, but in the present invention, silica treated with imidazole silane, aminosilane or epoxysilane (c). The surface roughness after the roughening treatment is such that the content ratio of the organic layered silicate (e) is 2 parts by weight or less, and a nonionic surfactant (d) is contained in a specific amount. The present invention has found that this can be further reduced.

In the prepreg according to the present invention, a porous substrate is impregnated with a resin composition. Therefore, the surface roughness of the cured product can be reduced by curing the resin composition impregnated in the porous substrate and then performing the roughening treatment. Therefore, when the metal layer of copper etc. by plating etc. is formed in the surface of hardened | cured material, the adhesiveness of the resin composition after hardening and a metal layer can be improved further.
Therefore, it is a member that forms a circuit by plating, for example, a member for forming an electronic circuit such as a build-up substrate, a member for forming a connection terminal such as a resin antenna, and has excellent reliability in the adhesion of the plating layer Can be obtained. The circuit can be formed by a known method such as etching.

The cured body according to the present invention is obtained by subjecting a resin composition configured according to the present invention or a cured resin obtained by heat curing a prepreg configured according to the present invention to a roughening treatment. The cured body has a plurality of holes having an average diameter of 5 μm or less on the surface, the surface roughness Ra of the cured body is 0.2 μm or less, and the surface roughness Rz is 2.0 μm or less. The surface roughness of the body is reduced.
Therefore, when a metal plating layer such as copper is formed on the surface of the cured product, the adhesion between the cured resin composition and the metal plating layer can be further enhanced. Moreover, since the surface roughness of the cured body is small, high-speed signal processing performance can be enhanced when a copper wiring having a small L / S value is formed on the cured body. Even if the signal becomes a high frequency of 5 GHz or more, the surface roughness of the surface of the cured body is small, so that there is an advantage that the loss of the electrical signal at the interface between the copper plating and the cured body is reduced. Further, since the anchor hole is as small as 5 μm or less, a pattern can be formed even if L / S is reduced. For example, even if L / S is 10/10 or less, since the anchor hole is small, there is no fear of a short circuit of the wiring, and a high-density wiring can be formed. In the present invention, although the surface roughness is small, the adhesion of the copper plating layer can be enhanced, which is a point that is greatly different from the prior art.

Furthermore, if the cured body according to the present invention is used, for example, in applications such as a resin-coated copper foil, a copper-clad laminate, a printed board, a prepreg, an adhesive sheet, and a TAB tape, a fine wiring can be formed. High-speed signal transmission can be improved.
Moreover, in the cured body according to the present invention, when the swelling treatment is performed before the resin cured product is roughened, the silica treated with imidazole silane, aminosilane, or epoxy silane is more easily detached. Can be made. Therefore, fine ruggedness can be formed on the surface of the cured body by releasing silica and forming fine pores.

In the sheet-like molded body according to the present invention, since the resin composition, prepreg, or cured body configured according to the present invention is used, the sheet-shaped molded body is excellent in mechanical strength such as tensile strength and linear expansion coefficient. The glass transition temperature Tg is also increased.
Moreover, in the laminated board which concerns on this invention, the adhesive layer which has a metal layer and / or adhesiveness is formed in the at least single side | surface of a sheet-like molded object. In this laminated board, the unevenness | corrugation surface of the surface of a sheet-like molded object, the adhesiveness of a metal layer and / or an adhesive layer, and a sheet-like molded object are improved, and it is excellent in adhesive reliability.
Furthermore, when the metal layer is formed as a circuit, the metal layer is firmly adhered to the surface of the sheet-like molded body, so that the reliability of the circuit made of the metal layer is enhanced.

  In the multilayer laminate according to the present invention, at least one kind of laminate selected from the laminates configured according to the present invention is laminated. Therefore, in the multilayer laminated board which concerns on this invention, the adhesiveness of a sheet-like molded object and a metal layer and / or an adhesive layer is improved. Further, when the resin composition is present at the lamination interface of the plurality of laminated plates, the bonding reliability between the laminated plates can be enhanced.

In the epoxy resin composition of the present invention, the epoxy resin (a), the epoxy resin curing agent (b), and any one or more of imidazole silane, amino silane, and epoxy silane are processed, and the average particle size is A resin composition containing silica (c) having a size of 5 μm or less and a nonionic surfactant (d), and a mixture (a + b) of an epoxy resin (a) and an epoxy resin curing agent (b) The silica (c) is contained in an amount of 25 to 400 parts by weight and the nonionic surfactant (d) is contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight.
Hereinafter, the epoxy resin composition of the present invention, a prepreg using the resin composition, a cured body, a sheet-like molded body, a laminate, a multilayer laminate, and the like will be described for each item.

1. Epoxy resin composition The epoxy resin composition of the present invention is treated with an epoxy resin (a), a curing agent for epoxy resin (b), and any one or more of imidazole silane, aminosilane, or epoxy silane, In addition, silica (c) having an average particle size of 5 μm or less and a nonionic surfactant (d) are contained as essential components, and if necessary, preferably an organically modified layered silicate (e) or further maleimide It contains the system compound (f) and other components.

(1) Epoxy resin (a)
In the present invention, the epoxy resin (a) refers to an organic compound having at least one epoxy group (oxirane ring).
The number of epoxy groups in the epoxy resin is preferably 1 or more per molecule, and more preferably 2 or more per molecule.
As the epoxy resin (a), conventionally known epoxy resins can be used, and examples thereof include the following epoxy resins (1) to (11).
These epoxy resins (a) may be used alone or in combination of two or more. Moreover, derivatives or hydrogenated products of these epoxy resins may be used as the epoxy resins.

Examples of the epoxy resin (1) which is an aromatic epoxy resin include bisphenol type epoxy resins and novolac type epoxy resins.
Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin. Moreover, as a novolak-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. are mentioned.
Examples of the epoxy resin (1) include an epoxy resin having an aromatic ring in the main chain such as naphthalene, naphthylene ether, biphenyl, anthracene, pyrene, xanthene, indole, an indole-phenol co-condensed epoxy resin, Examples thereof include phenol aralkyl type epoxy resins. In addition to this, an epoxy resin made of an aromatic compound such as trisphenolmethane triglycidyl ether can also be used.

  Examples of the epoxy resin (2) that is an alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3, for example. , 4-epoxy-2-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, and the like. As what is marketed among such an epoxy resin (2), the brand name "EHPE-3150" (softening temperature 71 degreeC) by Daicel Chemical Industries, etc. are mentioned, for example.

  Examples of the epoxy resin (3) which is an aliphatic epoxy resin include diglycidyl ether of neopentyl glycol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, and glycerin. Triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyoxyalkylene glycol containing an alkylene group having 2 to 9 carbon atoms (preferably 2 to 4 carbon atoms) And polyglycidyl ether of a long-chain polyol containing polytetramethylene ether glycol and the like.

  Examples of the epoxy resin (4) that is a glycidyl ester type epoxy resin include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, and salicylic acid. Glycidyl ether-glycidyl ester, dimer acid glycidyl ester and the like.

  Examples of the epoxy resin (5) which is a glycidylamine type epoxy resin include, for example, triglycidyl isocyanurate, N, N′-diglycidyl derivatives of cyclic alkylene urea, and N, N, O-triglycidyl of p-aminophenol. Derivatives, N, N, O-triglycidyl derivatives of m-aminophenol, and the like.

  Examples of the epoxy resin (6) that is a glycidyl acrylic epoxy resin include a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer such as ethylene, vinyl acetate, (meth) acrylic acid ester, and the like. Is mentioned.

  Examples of the epoxy resin (7) which is a polyester type epoxy resin include a polyester resin having one or more, preferably two or more epoxy groups per molecule.

  Examples of the epoxy resin (8) include unsaturated carbon double bonds in polymers mainly composed of conjugated diene compounds such as epoxidized polybutadiene and epoxidized dicyclopentadiene, or partially hydrogenated polymers thereof. Examples include epoxidized compounds.

  The epoxy resin (9) has a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a partially hydrogenated polymer block in the same molecule. Examples of the block copolymer include a compound obtained by epoxidizing a double bond portion of unsaturated carbon contained in a conjugated diene compound. Examples of such a compound include epoxidized SBS.

  Examples of the epoxy resin (10) include urethane-modified epoxy resins and polycaprolactone-modified epoxy resins in which urethane bonds and polycaprolactone bonds are introduced into the structures of the epoxy resins (1) to (9). Can be mentioned.

  Examples of the epoxy resin (11) include an epoxy resin having a bisarylfluorene skeleton. As what is marketed among such an epoxy resin (11), the brand name "Oncoat EX series" by Osaka Gas Chemical Co., etc. are mentioned, for example.

Moreover, when designing the low elastic component with a resin structure, a flexible epoxy resin is preferably used as the epoxy resin. As a flexible epoxy resin, what has a softness | flexibility after hardening is suitable.
Examples of the flexible epoxy resin include diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyoxyalkylene glycol and polytetramethylene ether glycol containing an alkylene group having 2 to 9 carbon atoms (preferably 2 to 4 carbon atoms), etc. Copolymers of polyglycidyl ethers and glycidyl (meth) acrylates of long-chain polyols containing ethylene and radical polymerizable monomers such as ethylene, vinyl acetate or (meth) acrylic acid esters, mainly conjugated diene compounds (co) Epoxidized unsaturated carbon double bond in polymer or partially hydrogenated (co) polymer, polyester resin having 1 or more, preferably 2 or more epoxy groups per molecule, urethane bond And introduced polycaprolactone bond Urethane-modified epoxy resin, polycaprolactone-modified epoxy resin, dimer acid-modified epoxy resin in which dimer acid or derivative thereof is introduced, epoxy group in rubber component such as NBR, CTBN, polybutadiene, acrylic rubber Examples thereof include a rubber-modified epoxy resin introduced.

  As the flexible epoxy resin, a compound having an epoxy group and a butadiene skeleton in the molecule is more preferably used. When a flexible epoxy resin having a butadiene skeleton is used, the flexibility of the resin composition and its cured product can be further increased, and the cured product can be stretched over a wide temperature range from a low temperature range to a high temperature range. The degree can be increased.

  In the epoxy resin composition of the present invention, the epoxy resin (a) has an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, and a biphenyl skeleton. It is preferable to contain at least 5% by mass of at least one selected from the group consisting of epoxy resins with respect to the total amount of epoxy resin. By containing 5 mass% or more, a glass transition temperature can be improved or a linear expansion coefficient can be reduced. Further, the total amount of the epoxy resin is at least one selected from the group consisting of an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, and an epoxy resin having a biphenyl skeleton. On the other hand, when the content is 5% by mass or more, the surface roughness after the roughening treatment can be further reduced.

  Further, the epoxy resin composition of the present invention includes the epoxy resin (a) which is an essential component, a curing agent (b) of the epoxy resin, silica treated with imidazole silane, aminosilane or epoxy silane (c). In addition to the nonionic surfactant (d), for example, a resin copolymerizable with the epoxy resin may be contained as necessary.

  The copolymerizable resin is not particularly limited, and examples thereof include phenoxy resin, thermosetting modified polyphenylene ether resin, and benzoxazine resin. These copolymerizable resins may be used alone or in combination of two or more.

  The thermosetting modified polyphenylene ether resin is not particularly limited. For example, a resin obtained by modifying a polyphenylene ether resin with a thermosetting functional group such as an epoxy group, an isocyanate group, or an amino group. Can be mentioned. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more. As an example of what was modified by the epoxy group among thermosetting modified polyphenylene ether resin, the brand name "OPE-2Gly" by Mitsubishi Gas Chemical Company etc. is mentioned, for example.

  The benzoxazine resin includes benzoxazine monomers or oligomers and those obtained by increasing the molecular weight by ring-opening polymerization of oxazine rings. The benzoxazine is not particularly limited, but, for example, one in which a substituent having an aryl group skeleton such as a methyl group, an ethyl group, a phenyl group, a biphenyl group, or a cyclohexyl group is bonded to the nitrogen of the oxazine ring, Or the thing etc. which the substituent which has arylene group frame | skeletons, such as a methylene group, ethylene group, phenylene group, biphenylene group, naphthalene group, cyclohexylene group, couple | bonded between nitrogen of two oxazine rings are mentioned. These benzoxazine monomers or oligomers and benzoxazine resins may be used alone or in combination of two or more.

(2) Curing agent for epoxy resin (b)
The epoxy resin composition of the present invention contains an epoxy resin curing agent (b) for curing the above epoxy resin (a).

  The blending ratio of the curing agent (b) in the resin composition is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin (a). If the curing agent (b) is less than 1 part by weight, the epoxy resin (a) may not be cured sufficiently, while if it is more than 200 parts by weight, it is excessive to cure the epoxy resin (a). Sometimes.

The curing agent (b) is not particularly limited, and conventionally known curing agents for epoxy resins can be used. For example, dicyandiamide, amine compounds, compounds synthesized from amine compounds, tertiary amine compounds, Examples include imidazole compounds, hydrazide compounds, melamine compounds, phenolic compounds, active ester compounds, benzoxazine compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, and derivatives thereof.
These hardening | curing agents may be used independently and 2 or more types may be used together. In addition to the curing agent, derivatives of these curing agents may be used as a resin curing catalyst such as acetylacetone iron.

Examples of the amine compound include a chain aliphatic amine compound, a cyclic aliphatic amine, and an aromatic amine.
Examples of the chain aliphatic amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, and polyoxypropylenetriamine.
Further, examples of the cycloaliphatic amine compound include mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, and N-aminoethylpiperazine. 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

Examples of the aromatic amine compound include m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p. -Diisopropyl benzene etc. are mentioned.
Moreover, as a compound synthesize | combined from the said amine compound, a polyaminoamide compound, a polyaminoimide compound, a ketimine compound etc. are mentioned, for example.
Furthermore, examples of the polyaminoamide compound include compounds synthesized from the amine compounds and carboxylic acids. Examples of the carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadioic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid, hexahydroisophthalic acid and the like.

Examples of the polyaminoimide compound include compounds synthesized from the amine compound and maleimide compound. Examples of the maleimide compound include diaminodiphenylmethane bismaleimide.
Moreover, as said ketimine compound, the compound etc. which are synthesize | combined from the said amine compound and a ketone compound are mentioned, for example.

  In addition, as a compound synthesized from the amine compound, for example, a compound synthesized from the amine compound and a compound such as an epoxy compound, a urea compound, a thiourea compound, an aldehyde compound, a phenol compound, or an acrylic compound. Is mentioned.

  Examples of the tertiary amine compound include N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1, 8-diazabiscyclo (5,4,0) undecene-1 etc. are mentioned.

Examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2' -Undecylimidazolyl- (1 ')]-ethyl s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl] -(1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl Examples include -4-methyl-5-hydroxymethylimidazole, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole.
The imidazole compound can be used not only as a curing agent but also as a curing accelerator in combination with other curing agents.

Examples of the hydrazide compound include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosane diacid dihydrazide, adipic acid dihydrazide, and the like. Is mentioned.
Examples of the melamine compound include 2,4-diamino-6-vinyl-1,3,5-triazine.
Furthermore, examples of the acid anhydride include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate. Tate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2,5- Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazelenic anhydride, polydodecanedioic acid Anhydride, Chloré De anhydride, and the like.

  The heat-latent cationic polymerization catalyst is not particularly limited, and examples thereof include benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt using antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like as a counter anion, Examples include ionic thermal latent cationic polymerization catalysts such as zendylsulfonium salts; nonionic thermal latent cationic polymerization catalysts such as N-benzylphthalimide and aromatic sulfonic acid esters.

  The photolatent cationic polymerization catalyst is not particularly limited, and examples thereof include aromatic diazonium salts, aromatic halonium salts, and aromatics using antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like as counter anions. Ionic photolatent cationic polymerization initiators such as onium salts such as sulfonium salts and organometallic complexes such as iron-allene complexes, titanocene complexes and arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, phosphate esters And nonionic photolatent cationic polymerization initiators such as phenolsulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide sulfonate.

Moreover, when the said hardening | curing agent has a phenol group, heat resistance, low water absorption, and dimensional stability can be improved.
Examples of the phenol compound having a phenol group include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, phenol aralkyl resin, and the like. These derivatives can also be used, and the phenol compound may be used alone or in combination of two or more.

When the curing agent is a phenol compound, the surface roughness (Ra, Rz) of the cured product becomes even finer when a roughening treatment is performed after the resin composition is cured.
When the curing agent is a phenol compound represented by any of the following formulas (1) to (3), the surface roughness (Ra, Rz) of the cured product is further reduced. Further, when the curing agent is a phenol compound, it is possible to obtain a cured product having high heat resistance, low water absorption, and further improved dimensional stability when giving a thermal history to the cured product. it can.

In the above formula (1), R ¹ represents a methyl group or an ethyl group, R ² represents hydrogen or a hydrocarbon group, and n represents an integer of 2 to 4.

  In said formula (2), n shows the integer of 0 or 1-5.

In the above formula (3), R ³ represents a group represented by the following formula (4a) or the following formula (4b), and R ⁴ represents the following formula (5a), the following formula (5b) or the following formula (5c). R ⁵ represents a group represented by the following formula (6a) or the following formula (6b), and R ⁶ represents hydrogen or a carbon atom-containing molecular chain group having 1 to 20 carbon atoms. P and q each represent an integer of 1 to 6, and r represents an integer of 1 to 11.

Curing agent represented by the above formula (3), when R ⁴ is a phenolic compound having a biphenyl structure represented by the formula (5c), the cured product, electrical properties, low linear expansion coefficient, heat resistance, In addition to being excellent in various physical properties such as low water absorption, the dimensional stability can be further improved when a heat history is given to the cured product. Among these, those having a structure represented by the following formula (7) are preferable because these performances can be further improved.

  In said formula (7), n shows the integer of 1-11.

  Examples of the active ester compound include aromatic polyvalent ester compounds. Since the active ester group does not generate an OH group upon reaction with the epoxy resin, it is said that a cured product having excellent dielectric constant and dielectric loss tangent can be obtained. For example, disclosed in JP-A-2002-12650 Has been. Examples of commercially available products include trade name “EPICLON EXB9451-65T” manufactured by Dainippon Ink and Chemicals, Inc. When such an active ester compound is used, a cured product having excellent dielectric constant and dielectric loss tangent can be obtained.

  Examples of the benzoxazine compound include aliphatic benzoxazines and aromatic benzoxazine resins. Examples of commercially available products include trade names “Pd type benzoxazine” and “Fa type benzoxazine” manufactured by Shikoku Kasei Kogyo Co., Ltd.

In addition to the imidazole compound described above, the resin composition includes a phosphine compound such as triphenorphosphine, or DBU, DBN, and its phenol salt, octylate, p-toluenesulfonate, formate, orthophthalate, A curing accelerator such as a phenol novolac resin salt may be added.
Cyanate ester resins can also be used. As the cyanate ester resin, a cured product having a low linear expansion coefficient can be obtained. For example, a novolac type sinate ester resin, a bisphenol type cyanate ester resin, a prepolymer obtained by partially triazine conversion, and the like can be used.

In the epoxy resin composition of the present invention, the epoxy resin curing agent (b) includes a curing agent having a biphenyl skeleton, an active ester curing agent, a curing agent having a benzoxazine structure, a curing agent having an aminotriazine skeleton, and It is preferable to contain 5% by mass or more of at least one selected from the group consisting of curing agents having a naphthalene skeleton with respect to the total amount of the curing agent for epoxy resin.
The epoxy resin composition preferably contains at least one of a phenolic curing agent having a biphenyl structure (or skeleton), an active ester curing agent, and a curing agent having a benzoxazine structure as a curing agent. . Furthermore, it is particularly preferable that the epoxy resin composition contains at least one of a phenolic curing agent or an active ester curing agent having a biphenyl structure. In this case, since the curing agent has a biphenyl structure or an active ester structure, for example, the resin itself is hardly affected in the swelling / roughening treatment as a pretreatment for plating. Therefore, when the resin composition is cured and then roughened, the surface of the resin is not roughened, and the silica treated with imidazole silane, aminosilane or epoxysilane having an average particle size of 5 μm or less is selectively detached. Thus, a hole is formed. Therefore, an uneven surface having a very small surface roughness can be formed on the surface of the cured product.

  When the molecular weight of the epoxy resin (a) and / or the curing agent (b) is large, it is easy to form a fine rough surface on the surface of the cured product. Therefore, the weight average molecular weight of the epoxy resin (a) is 4000 or more. The weight average molecular weight of the curing agent (b) is preferably 1800 or more. In particular, the molecular weight of the curing agent is important for forming a fine rough surface.

  Moreover, if the epoxy equivalent of the epoxy resin and / or the equivalent of the curing agent is large, it is easy to form a fine rough surface on the surface of the cured product.

  When the epoxy resin and / or phenol curing agent has a biphenyl structure, the cured product obtained by curing the resin composition is excellent in electrical characteristics, in particular, dielectric loss tangent, excellent in strength and linear expansion coefficient, and in water absorption. Also lower. When the curing agent has an aromatic polyvalent ester structure or a benzoxazine structure, a cured product having further excellent dielectric constant and dielectric loss tangent can be obtained. Further, when a low linear expansion coefficient is required, anthracene type epoxy resin, naphthalene type epoxy resin, cyanate ester resin and the like are suitable.

  In the biphenyl type epoxy resin, a part of the hydroxyl groups of the hydrophobic phenol compounds of the above formulas (1) to (7) are substituted with an epoxy group-containing group, and the remainder is a substituent other than the hydroxyl group, for example, hydrogen. And a biphenyl type epoxy resin represented by the following formula (8) is preferably used.

  In said formula (8), n shows the integer of 1-11.

(3) Silica treated with imidazole silane, amino silane or epoxy silane (c)
The epoxy resin composition of the present invention contains silica (c) that has been treated with imidazole silane, aminosilane, or epoxy silane and has an average particle size of 5 μm or less.
The mixing ratio of the silica (c) treated with imidazole silane, aminosilane or epoxysilane in the resin composition is 25 to 100 parts by weight of the mixture (a + b) composed of the epoxy resin (a) and the curing agent (b). 400 parts by weight is blended. The blending ratio of silica is preferably in the range of 25 to 250 parts by weight, and more preferably in the range of 43 to 150 parts by weight with respect to the mixture. When the amount of silica is less than 25 parts by weight, the total surface area of the holes formed by the removal of silica by roughening treatment or the like is reduced, and sufficient plating adhesion strength is not expressed. Resin tends to be brittle.

  In addition, in the silica (c) treated with imidazole silane, amino silane or epoxy silane, the treatment amount with imidazole silane, amino silane or epoxy silane is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of silica. Preferably it is 2-4 weight part. When the amount of treatment such as imidazole silane is less than 0.1 parts by weight, the surface roughness of the rough surface increases because the amount of treatment is insufficient. On the other hand, when the amount exceeds 5 parts by weight, imidazole group, amino group or The absolute amount of the epoxy group increases, and the storage stability of the resin composition is deteriorated (easily gelled).

As the imidazole silane, a silane coupling agent having an imidazole group disclosed in JP-A Nos. 9-169871, 2001-187836, 2002-128872, and the like can be appropriately used. it can.
The silane coupling agent is a compound composed of an organic substance and silicon, but imidazole silane is a coupling agent having an imidazole group in the molecule. The imidazole silane preferably has a structure having no hydroxyl group in the molecule. This is because the imidazole silane compound having a hydroxyl group has a problem of poor stability when mixed with an epoxy resin and stored. Specific examples of the imidazole silane that does not contain a hydroxyl group include “IM-1000” manufactured by Nikko Metal Co., Ltd.

  Examples of the aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyl. Examples include trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-β (aminoethyl) γ-aminopropyltriethoxysilane.

Furthermore, examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane and the like.
As the silane coupling agent, not only the surface treatment of silica but also a silane coupling agent can be separately added to the resin composition and are included in the scope of the present invention. In particular, it is possible to reduce the surface roughness after the roughening treatment by further adding an imidazole silane coupling agent. The amount of the silane coupling agent to be added is desirably 5 parts by weight or less with respect to the total amount of the resin composition. This is because when the amount is 5 parts by weight or more, the viscosity is changed, or the mechanical properties of the cured product are deteriorated.

  Examples of the silica include crystalline silica obtained by pulverizing natural silica raw material, crushed fused silica obtained by flame melting / pulverization, spherical fused silica obtained by flame melting / pulverization / flame melting, fumed silica (Aerosil ), Or synthetic silica such as sol-gel silica. Since synthetic silica often contains ionic impurities, fused silica is preferably used in terms of purity. Silica slurry in which silica particles are dispersed in a solvent is advantageous in terms of workability and productivity and can be used.

  Examples of the shape of silica include a true spherical shape and an indefinite shape. When the roughened resin is subjected to a roughening treatment, the silica is more easily detached, so that it is preferably spherical.

  In the present invention, silica having an average particle size of 5 μm or less is used to obtain a fine rough surface. The pores on the surface of the cured product (cured body) are those from which silica having an average particle diameter of 5 μm or less is detached, and thus the average diameter of the holes is about 5 μm or less. However, if the average particle diameter is larger than 5 μm, it becomes difficult for silica to be detached when the resin-cured product is subjected to a roughening treatment, and the pores formed in the detached portion become larger, resulting in a rough surface roughness. Become. In particular, when the epoxy resin or the curing agent has a phenol, biphenyl structure, aromatic polyvalent ester structure, benzoxazine structure, or the like that is difficult to be processed by roughening treatment, desorption occurs as the silica particle size increases. It becomes difficult.

The average particle diameter of silica is preferably 1 μm or less. When the average particle size is 1 μm or less, when the roughened resin is subjected to a roughening treatment, silica is more easily detached, and the pores formed on the surface of the detached cured product are further reduced. When the average particle diameter of the silica is 1 μm or less, the particles are easily aggregated, and it becomes clear that the dispersibility is insufficient only by treating the silica with an imidazole silane coupling agent. As a result of their intensive studies, the dispersibility can be improved by using the nonionic surfactant (d) described in detail in the next section. As a result, even if the amount of silica added increases, It became possible to form a rough surface.
As the average particle diameter of silica, a median diameter (d50) value of 50% can be adopted, and it can be measured with a laser diffraction scattering type particle size distribution measuring apparatus.

  In the present invention, silicas having different average particle diameters may be used in combination. Considering fine packing, by using a plurality of types of silica having different particle size distributions, it can be suitably used even in applications requiring fluidity, such as a component-embedded substrate.

  The maximum particle diameter of silica is preferably 5 μm or less. When the maximum particle size is 5 μm or less, when the resin composition is subjected to a roughening treatment, silica is more easily detached, and relatively coarse irregularities are not formed on the surface of the cured product. Unevenness can be formed. In particular, when the epoxy resin or the curing agent has a biphenyl structure or an aromatic polyvalent ester structure, a benzoxazine structure, or the like that is difficult to be processed by a roughening treatment, the roughening liquid is difficult to penetrate from the surface of the cured product. When the maximum particle diameter of silica is 5 μm or less, silica is easily detached.

The specific surface area of silica is preferably 3 m ² / g or more. When the specific surface area is smaller than 3 m ² / g, for example, when a metal plating layer such as copper is formed on the surface of the cured product, the adhesion between the cured product and the metal plating may not be sufficient. There is a risk that the physical characteristics will deteriorate. The specific surface area can be determined by the BET method.

Examples of the method for treating silica using imidazole silane, aminosilane, or epoxy silane include the following methods.
A method called a dry method is mentioned, and a method of directly attaching a silane compound to silica is an example. Specifically, silica is charged into a mixer, and alcohol or an aqueous solution of imidazole silane, aminosilane, or epoxy silane is dropped or sprayed with stirring, followed by stirring and classification with a sieve. Furthermore, the silane compound and the silica can be dehydrated and condensed by heating to obtain silica treated with imidazole silane, aminosilane, or epoxysilane.

Another method includes a method called a wet method. As an example, imidazole silane, amino silane or epoxy silane is added while stirring the silica slurry, further stirring, classification by filtration, drying and sieving, and dehydration condensation of the silane compound and silica by heating. Thus, silica treated with imidazole silane, amino silane or epoxy silane can be obtained.
Furthermore, as another method, it is also possible to add imidazole silane, aminosilane, or epoxy silane while stirring the silica slurry, and then proceed to dehydration condensation by heating and refluxing to use as a silica slurry.

  Compared to the case of using untreated silica, in the case of using silica treated with imidazole silane, aminosilane, or epoxy silane, when the resin composition is cured, the silica is combined with the epoxy resin. Increases the glass transition temperature Tg by 10 to 15 ° C. That is, a cured product having a high glass transition temperature Tg can be obtained by including silica (c) treated with imidazole silane, aminosilane or epoxy silane in the resin composition instead of untreated silica. . Moreover, the reflow resistance of a hardening body can be improved by using the silica by which the imidazole silane, the aminosilane, or the epoxy silane process was used.

(4) Nonionic surfactant (d)
The epoxy resin composition of the present invention contains a nonionic surfactant (d).
As the nonionic surfactant (d), ether-based, ester-based, ester-ether-based, nitrogen-containing compounds, and various fatty acids such as stearic acid, oleic acid, linoleic acid, and ricinoleic acid are also suitable. Can be used.

  Examples of the ether surfactant include polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, polyoxyethylene behenyl ether, polyoxyethylene cholesteryl ether , Polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene alkyl ether such as polyoxyethylene decyl tetradecyl ether, polyoxyethylene alkylphenyl ether, and the like.

  Examples of the ester surfactant include glycerin fatty acid ester, polyglycerin condensed ricinoleic acid ester, polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester, sorbitan fatty acid ester, And sucrose fatty acid esters.

  Examples of the glycerin fatty acid ester include mono-distearic acid diglycerin, monostearic acid diglycerin, mono-dioleic acid diglycerin, monostearic acid hexaglycerin, monooleic acid hexaglycerin, monomyristic acid hexaglycerin, monolauric acid hexa Glycerin, mono-dicaprylic acid hexaglycerin, hexastearic acid hexaglycerin, octastearic acid hexaglycerin, monostearic acid decaglycerin, distearic acid decaglycerin, pentastearic acid decaglycerin, decastearic acid decaglycerin, monooleic acid decaglycerin, Penaoleic acid decaglycerin, dekaoleic acid decaglycerin, monomyristic acid decaglycerin, monolauric acid decaglycerin, Triglycerol laurate, Triglycerol monomyristate, Triglycerol monooleate, Triglycerol monostearate, Pentaglycerol monolaurate, Pentaglycerol monomyristate, Pentaglycerol trimyristate, Pentaglycerol monooleate, Penta trioleate Examples thereof include glycerin, pentaglyceryl monostearate, pentaglyceryl tristearate, and pentaglycerin hexastearate.

Examples of the polyglycerin condensed ricinoleic acid ester include condensed ricinoleic acid tetraglycerin, condensed ricinoleic acid hexaglycerin, condensed ricinoleic acid pentaglycerin and the like.
Examples of the polyglycerin ethylene glyceryl ether fatty acid ester include polyoxyethylene glyceryl distearate, polyoxyethylene glyceryl tristearate, polyoxyethylene glyceryl isostearate, polyoxyethylene glyceryl trioleate, and the like.

Examples of the polyoxyethylene hydrogenated castor oil fatty acid ester include polyoxyethylene hydrogenated castor oil lauric acid, polyoxyethylene hydrogenated castor oil isostearate, polyoxyethylene hydrogenated castor oil triisostearate, and the like.
Examples of the polyoxyethylene trimethylolpropane fatty acid ester include, for example, polyoxyethylenetrimyristate trimethylolpropane, polyoxyethylene distearate trimethylolpropane, polyoxyethylenetristearate trimethylolpropane, polyoxyethylenetriisostearin. Examples include acid trimethylolpropane.

Examples of the ester / ether type surfactant include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol isostearate, polyethylene glycol monooleate, polyoxyethylene glyceryl monostearate, polyoxyethylene castor oil, polyoxyethylene Ethylene hydrogenated castor oil, polyoxyethylene sorbit sorbitan fatty acid ester, stearic acid polyoxyethylene lauryl ether, isostearic acid polyoxyethylene lauryl ether, stearic acid polyoxyethylene cetyl ether, stearic acid polyoxyethylene stearyl ether, dilauric acid polyethylene glycol , Polyethylene glycol distearate, polyethylene diisostearate Recall, polyethylene glycol, and the like dioleate.
It is important to disperse the nonionic surfactant sufficiently, and it is important to add a solvent nonionic surfactant containing silica treated with imidazole silane, aminosilane or epoxy silane and to sufficiently stir. In the case of silica slurry, it is preferable to add a nonionic surfactant in advance and stir well. The stirring may be performed using a disper or a bead mill.

  In the epoxy resin composition of the present invention, the content of the nonionic surfactant (d) is preferably in the range of 0.1 to 10 parts by weight. If the amount is less than 0.1 part by weight, the dispersibility is not sufficient, while if it exceeds 10 parts by weight, the mechanical properties and electrical properties of the cured product are adversely affected. It is more preferable that the content of the nonionic surfactant (d) is 0.5 to 2 parts by weight because it hardly affects the electric characteristics.

(5) Organized layered silicate (e)
The epoxy resin composition of the present invention preferably contains an organized layered silicate (e).
When the resin composition contains the organically modified layered silicate (e) and the silica (c) treated with imidazole silane, aminosilane or epoxysilane, the organically modified layered silicate exists around the silica. become. In this case, the resin composition is heated and cured, and further subjected to swelling and roughening treatment, for example, to further easily remove silica treated with imidazole silane, aminosilane, or epoxy silane present on the surface of the resin cured product. Can be separated. The mechanism by which silica is easily detached is not clear, but the swelling liquid or roughening liquid permeates from the interface between the organically modified layered silicate or from the nano-ordered interface between the organically modified layered silicate and the resin. At the same time, it is presumed to penetrate into the interface between the epoxy resin (a) and silica (c) treated with imidazole silane.

  The blending ratio of the organically modified layered silicate (e) in the resin composition is preferably in the range of 2 parts by weight or less with respect to 100 parts by weight of the mixture (a + b) composed of the epoxy resin (a) and the curing agent (b). . When the organic layered silicate is more than 2 parts by weight, especially when the amount of silica treated with imidazole silane, aminosilane or epoxysilane is 25 parts by weight or more, the interface through which the swelling liquid or the roughening liquid permeates increases. This is because the surface roughness becomes relatively large. On the other hand, when no organic layered silicate is added, the surface roughness can be further reduced.

  In this specification, the organically modified layered silicate refers to a layered silicate that has been subjected to a known organic treatment for the purpose of improving the dispersibility in the resin and the cleaving property.

Examples of layered silicates include smectite clay minerals, swellable mica, vermiculite, and halloysite. Examples of smectite clay minerals include montmorillonite, hectorite, saponite, beidellite, stevensite, and nontronite.
Among these, at least one selected from the group consisting of montmorillonite, hectorite, and swellable mica is preferably used as the layered silicate. These layered silicates may be used alone or in combination of two or more.

Although the compounding ratio of the organically modified layered silicate (e) has been described above, it can be appropriately set according to the use of the resin composition.
For example, when the resin composition is used for sealing agents, the blending ratio of the organically modified layered silicate is based on 100 parts by weight of the mixture (a + b) composed of the epoxy resin (a) and the curing agent (b). The range of 2 parts by weight or less is preferable. If the blending ratio is more than 2 parts by weight, the permeation rate of the swelling liquid and the roughening liquid will be high, so that the surface roughness will change too fast and sufficient processing time for the swelling treatment and roughening treatment cannot be secured. May occur. By adjusting the temperature of swelling treatment and roughening treatment, it is possible to increase the treatment time to some extent.

  When blended in the resin composition such that the silica is 25 to 400 parts by weight and the organically modified layered silicate is 2 parts by weight or less with respect to 100 parts by weight of the mixture comprising the epoxy resin and the curing agent, a sheet-like shape When the substrate formed by curing the resin composition of the present invention formed on the substrate is perforated by a laser such as a carbon dioxide gas laser, an epoxy resin component or an epoxy resin curing agent component and a layered silicate component At the same time, they decompose and evaporate, and the resin-derived components and inorganic residues that remain partially become extremely small. Therefore, when the desmear treatment is performed, the remaining layered silicate residue can be easily removed without performing the treatment a plurality of times or in combination of a plurality of types. Therefore, generation | occurrence | production of a plating defect etc. can be suppressed with the residue which generate | occur | produces by a drilling process. In addition, a known method can be used for the desmear process, for example, it can carry out by a plasma process, a chemical | medical solution process, etc.

(6) Maleimide compound (f)
The epoxy resin composition of the present invention preferably further contains a maleimide compound (f).
The maleimide (maleic imide) compound (f) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. For example, N-phenylmaleimide, N-hydroxyphenyl Maleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl -5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. 1 type or 2 or more types may be used by appropriately mixing It can be. More preferred are bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane And polyphenylmethanemaleimide. Specific examples thereof include bis (4-maleimidophenyl) methane (or 4,4′-Diphenylmethyl bismaleimide) under the trade name “BMI-1000” manufactured by Daiwa Kasei Kogyo Co., Ltd., and the trade name “BMI-2000”. ”Polyphenylmethanemaleimide (or oligomer of phenylmaleimide), bis (3-ethyl-5-methyl-4-maleimidophenyl) methane with the trade name“ BMI-5100 ”, and products made by Kay Kasei Co., Ltd. Bis (4-maleimidophenyl) methane (or 4,4′-Diphenylmethane bismaleimide) with the name “BMI”, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane with the trade name “BMI-70” (or Bi s- (3-ethyl-5-methyl-4-maleimidephenyl) methane), 2,2-bis {4- (4-maleimidophenoxy) phenyl} propane (or 2,2′-) under the trade name “BMI-80” Bis- [4- (4-maleimidephenoxy) phenyl] propane).

When the maleimide compound (f) is contained in the epoxy resin composition, the thermal expansion characteristics, the metal foil peeling strength, the glass transition temperature (Tg), the heat resistance at the time of moisture absorption and flame retardancy are excellent. Demonstrate the effect.
In the epoxy resin composition of the present invention, the content ratio of the maleimide compound (f) is 2 to 45% by mass, preferably 5 to 25% by mass, based on the total amount of the resin composition.
If the content of the maleimide compound (f) is less than 2% by mass, the addition effect is not obtained. On the other hand, if the content of the maleimide compound (f) exceeds 45% by mass, the surface roughness after the roughening treatment is obtained. There is a concern that the tensile strength and elongation of the cured product will decrease.

(7) Other components In the epoxy resin composition of the present invention, thermoplastic resins, thermoplastic elastomers, cross-linked rubbers, oligomers, inorganic compounds are included as long as the object of the present invention is not impaired. Nucleating agents, antioxidants, anti-aging agents, heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, and Additives such as colorants may be blended. These may be used independently and 2 or more types may be used together.

  Examples of the resin composition include at least one thermoplastic resin selected from the group consisting of a polysulfone resin, a polyether sulfone resin, a polyimide resin, and a polyetherimide resin, a polyvinyl benzyl ether resin, and a bifunctional polyphenylene ether oligomer At least one kind of thermosetting resin selected from the group consisting of a reaction product (Mitsubishi Gas Chemical trade name “OPE-2St”) obtained by the reaction between chloromethylstyrene and chloromethylstyrene may be added. These thermocomposable resins and thermosetting resins may be used alone or in combination of two or more. The blending ratio of the thermoplastic resin or thermosetting resin in the resin composition is preferably in the range of 0.5 to 50 parts by weight, and in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin (a). More preferred. If the thermoplastic resin or thermosetting resin is less than 0.5 parts by weight, the elongation and toughness may not be sufficiently improved, and if it is more than 50 parts by weight, the strength may decrease.

(8) Production and use of epoxy resin composition The production method of the epoxy resin composition of the present invention is not particularly limited. For example, a mixture of an epoxy resin (a) and a curing agent (b); Silica (c) and nonionic surfactant (d) treated with imidazole silane, amino silane or epoxy silane, and organic layered silicate (e) or further maleimide compound (f), if necessary, as a solvent After adding, the method of drying and removing a solvent is mentioned.

The epoxy resin composition of the present invention is used, for example, dissolved in an appropriate solvent or molded into a film. The application of the resin composition is not particularly limited. For example, a substrate material, a sheet, a laminate, a resin-coated copper foil, a copper-clad laminate, a TAB tape for forming a core layer, a buildup layer, etc. of a multilayer substrate It is suitably used for printed circuit boards, prepregs, varnishes and the like.
In addition, when the roughening treatment is performed after the resin composition is cured, the roughness of the surface formed by the roughening treatment is smaller than the conventional one. Become thicker. Further, since the surface roughness is small, the thickness of the insulating layer can be reduced.
Therefore, when the resin composition is used for applications requiring insulation such as copper foil with resin, copper-clad laminate, printed circuit board, prepreg, adhesive sheet and TAB tape, fine wiring can be formed. . Therefore, the signal transmission speed can be increased.
When the resin composition of the present invention is used for an additive method for forming a circuit after conducting conductive plating, a build-up substrate for forming a resin and a conductive plating layer in multiple layers by a semi-additive method, etc. This is preferable because the reliability of the joint surface between the conductive plating layer and the resin is increased.

  When a resin material is used to produce a substrate material, sheet, laminate, resin-coated copper foil, copper-clad laminate, TAB tape, printed circuit board, prepreg, or adhesive sheet, it is produced through multiple steps. Even in such a case, it can be manufactured at a high yield, and barrier properties such as adhesiveness, electrical properties, high-temperature properties, dimensional stability (low linear expansion coefficient), and moisture resistance can be improved. In the present specification, the sheet includes a film-like sheet having no self-supporting property.

  The molding method is not particularly limited. For example, extrusion molding after melt kneading in an extruder and extrusion into a film using a T die or a circular die; dissolved in a solvent such as an organic solvent Alternatively, after being dispersed, a casting molding method of casting to form a film, other conventionally known film molding methods, and the like can be mentioned. Especially, when a multilayer printed circuit board is produced using the resin sheet which consists of the resin composition of this invention, since thickness reduction can be advanced, the extrusion molding method and the casting molding method are used suitably.

  The resin composition configured according to the present invention can be applied to a sealing material, a solder resist, and the like. In addition, the resin composition of the present invention can be suitably used for applications requiring high-frequency characteristics such as a passive component or a component-embedded substrate in which an active component is embedded because the resin composition of the present invention is excellent in high-speed signal transmission performance. .

2. Prepreg The prepreg of the present invention is constituted by impregnating a porous base material with the above epoxy resin composition. The material of the porous substrate is not particularly limited as long as the resin composition can be impregnated, and examples thereof include organic fibers such as carbon fibers, polyamide fibers, polyaramid fibers, and polyester fibers, and glass fibers. Moreover, as the form, textiles, such as a plain weave and a twill weave, and a nonwoven fabric are mentioned. Of these, a glass fiber nonwoven fabric is preferred.

3. Cured body When the epoxy resin composition of the present invention or the prepreg impregnated with the epoxy resin composition is heated and cured, a cured body can be obtained. The cured product generally means a range from a semi-cured product in a semi-cured state called a B stage to a cured product in a completely cured state.
The cured product of the present invention is obtained, for example, as follows.
When the resin composition is heated at, for example, 160 ° C. for 30 minutes, a semi-cured product in the middle of the reaction is obtained. Furthermore, when this semi-cured product is heated at a high temperature, for example, at 180 ° C. for 1 to 2 hours, a cured product that is almost completely cured is obtained.

In order to form fine irregularities on the surface of the obtained cured resin, for example, a roughening treatment, or a swelling treatment and a roughening treatment are performed.
As the swelling treatment method, for example, a treatment method using an aqueous solution of a compound mainly composed of ethylene glycol or the like or an organic solvent dispersion solution is used. More specifically, the swelling treatment is performed, for example, by treating the cured resin with a 40 mass% ethylene glycol aqueous solution at a treatment temperature of 30 to 85 ° C for 1 to 20 minutes.

The roughening treatment includes, for example, manganese compounds such as potassium permanganate and sodium permanganate, chromium compounds such as potassium dichromate and anhydrous potassium chromate, sodium persulfate, potassium persulfate, and ammonium persulfate. A chemical oxidant mainly composed of a persulfate compound is used. These chemical oxidants are used, for example, in an aqueous solution or an organic solvent dispersion.
Although it does not specifically limit as a roughening processing method, For example, 30-90 g / L permanganic acid or a permanganate solution, 30-90 g / L sodium hydroxide solution is used, Processing temperature 30-85 degreeC, 1 A method of treating the cured product once or twice in 10 minutes is preferable. When the number of treatments is large, the roughening effect is large, but when the treatment is repeated, the surface of the resin is also shaved. When the roughening treatment is performed three times or more, the roughening effect due to the increase in the number of treatments may not be substantially changed, or it may be difficult to form clear irregularities on the surface of the cured body. is there.

The cured product obtained as described above preferably has a surface roughness Ra of 0.2 μm or less and a surface roughness Rz of 2.0 μm or less. When silica (c) treated with imidazole silane, aminosilane or epoxy silane has an average diameter of 1 μm or less, it has a plurality of pores with an average diameter of 5 μm or less, and surface roughness Ra is 0.15 μm or less. In addition, the surface roughness Rz is preferably 1.5 μm or less.
In the present invention, as described above, dispersibility can be improved by using silica (c) treated with imidazole silane, amino silane or epoxy silane and nonionic surfactant (d). Even if the amount of silica added is increased, a fine rough surface can be formed.
When the average diameter of the plurality of holes is larger than 5 μm, it becomes easy to short-circuit between the wires when L / S becomes small, and it becomes difficult to form a fine circuit. When the surface roughness Ra is larger than 0.2 μm, The signal transmission speed may not be increased. If the surface roughness Rz is larger than 2.0 μm, the transmission speed of the electric signal may not be increased. The surface roughness Ra, Rz can be determined by a measuring device or the like based on the measuring method of JIS B0601-1994.

  As the average particle size of silica contained in the resin composition is smaller, finer irregularities are formed. Therefore, a resin composition containing silica having a small average particle size is very useful because it can increase the speed of signal processing in copper wiring with a short L / S. When the average particle diameter of silica is smaller, for example, when L / S indicating the fineness of circuit wiring is 65/65 μm or smaller than 45/45 μm, the average particle diameter of silica is preferably 5 μm or less, more preferably Is 2 μm or less, and when L / S is finer than 13/13 μm, it is preferably 2 μm or less, more preferably 1 μm or less.

  The hardened body after the roughening treatment can be subjected to electrolytic plating after being subjected to a known plating catalyst or electroless plating, if necessary.

  Also, in the vicinity of the surface of the pores from which the silica has been detached, a curing reaction with imidazole proceeds and the mechanical strength seems to be very strong. Therefore, when a plating layer such as copper is formed, the strength in the vicinity of the surface of the hole that maintains the anchor effect is maintained in addition to the shape anchor effect. A copper plating layer having high adhesion can be formed on the cured body having a polyvalent ester structure or a benzoxazine structure. In combination with nonionic surfactant (d), dispersibility of silica treated with imidazole silane, aminosilane or epoxy silane is improved, and a large amount of silica is blended to reduce the linear expansion coefficient. Even in this case, it is possible to develop stable plating adhesion without causing local strength reduction due to silica aggregation.

4). Sheet-like molded object, laminated board, and multilayer laminated board The sheet-like molded object which concerns on this invention shape | molds the resin composition, a prepreg, or a hardening body in the shape of a sheet | seat. Examples of the sheet-like molded body include a sheet having a film-like shape and an adhesive sheet.
Moreover, the laminated board which concerns on this invention has the adhesive layer which has a metal layer and / or adhesiveness formed in the at least single side | surface of a sheet-like molded object.
Furthermore, the multilayer laminated board which concerns on this invention laminates | stacks at least 1 type of laminated board chosen from said laminated board.

  In addition, the sheet | seat, laminated board, etc. which were mentioned above may be laminated | stacked with the film which can be released | released with a sheet | seat, a laminated body, etc. for the purpose of conveyance assistance, prevention of dust adhesion, and a damage, etc. Examples of the film having properties include resin-coated paper, polyester film, polyethylene terephthalate (PET) film, polypropylene (PP) film, and the like, and may be further subjected to mold release treatment as necessary.

  As the mold release treatment method, the film contains a silicon compound, a fluorine compound, a surfactant, or the like, or a process for imparting unevenness to the surface so as to have mold release properties, such as embossing of satin. Examples thereof include a method of applying a releasable substance such as a silicon compound, a fluorine compound, and a surfactant on the surface. In order to further protect the film having releasability, a protective film such as a resin-coated paper, a polyester film, a PET film, or a PP film may be laminated on the film.

  Resin composition, prepreg, cured product thereof, and substrate material, sheet-like molded body, laminate, resin-coated copper foil, copper-clad laminate, TAB tape, printed circuit board, multilayer laminate, adhesive sheet For example, a metal layer can be formed on at least one surface, for example, as a circuit.

  As the metal, a metal foil or metal plating used for shielding, circuit formation or the like, or a plating material used for circuit protection can be used. Examples of the plating material include gold, silver, copper, rhodium, palladium, nickel, tin and the like. These may be two or more kinds of alloys. May be. Furthermore, other metals and substances may be included for improving the characteristics according to the purpose.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to a following example.

(Materials used):
In the examples and comparative examples, the following raw materials were used.
1. Epoxy resin:
Biphenyl skeleton-containing epoxy resin (Nippon Kayaku Co., Ltd., trade name “NC-3000H”, weight average molecular weight 2070, epoxy equivalent 288) (corresponding to the formula (8))
-Bisphenol A type epoxy resin (trade name “YD-8125”, manufactured by Tohto Kasei Co., Ltd., weight average molecular weight about 350)
・ Bisphenol F type epoxy resin (Nippon Kayaku Co., Ltd., trade name “RE-304S”)
・ Anthracene skeleton-containing epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name “YX8800”, epoxy equivalent 181)
・ Naphthalene skeleton-containing epoxy resin (DIC (formerly Dainippon Ink Industries), trade name “HP4700”, epoxy equivalent 165)
・ Adamantane skeleton-containing epoxy resin (manufactured by Idemitsu Kosan Co., Ltd., trade name “adamantate X-E-202”, epoxy equivalent 193)
-Triazine skeleton-containing epoxy resin (manufactured by Nissan Chemical Industries, trade name "TEPIC-PAS B22", epoxy equivalent 180-200)

2. Curing agent for epoxy resin:
A phenolic curing agent comprising the hydrophobic phenol compound represented by the formula (7) (Maywa Kasei Co., Ltd., trade name “MEH7851-4H”, weight average molecular weight 10200 in terms of Pst)
Active ester compound type curing agent (manufactured by DIC (former Dainippon Ink and Industries), trade name “EXB-9451-65T”, weight average molecular weight 2840 in terms of Pst)
Average molecular weight 2840)
Aminotriazine novolak phenol type curing agent (manufactured by DIC (former Dainippon Ink Industries), trade name “LA-1356”, 60% by mass MEK solution)
・ Α-naphthol type phenol curing agent (trade name “SN-475”, softening point 75 ° C., manufactured by Tohto Kasei Co., Ltd.)
3. Curing accelerator:
・ Imidazole (made by Shikoku Kasei Kogyo Co., Ltd., trade name “2MAOK-PW”)

4). Organized layered silicate:
・ Synthetic hectorite chemically treated with trioctylmethylammonium salt (trade name “Lucentite STN” manufactured by Co-op Chemical)

5. Organic solvent:
・ N, N-dimethylformamide (DMF, special grade, manufactured by Wako Pure Chemical Industries, Ltd.)

6). silica:
・ Silica (manufactured by Tatsumori Co., Ltd., trade name “1-Fx”, average particle size 0.38 μm, maximum particle size 1 μm, surface area 30 m ² / g)
7). Silica surface treatment agent:
・ Imidazolesilane having no hydroxyl group in the molecule (manufactured by Nikko Materials, trade name “IM-1000”)
・ Imidazolesilane having a hydroxyl group in the molecule (manufactured by Nikko Materials, trade name “IS-1000”)
・ Aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-903”)
・ Epoxysilane (Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”)
・ Vinylsilane (made by Shin-Etsu Chemical Co., Ltd., trade name “KBM-1003”)

(Silica imidazole silane treatment method etc.):
100 parts by weight of silica, 4 parts by weight of imidazole silane having no hydroxyl group in the molecule and 100 parts by weight of ethanol were mixed and stirred at 60 ° C. for 1 hour, and then volatile components were distilled off. Then, it dried at 100 degreeC and 6 hours with the vacuum dryer, and obtained the silica (1) which is an imidazole silane processing filler which does not have a hydroxyl group in a molecule | numerator. Moreover, the silica (2) which is an imidazole silane processing filler which has a hydroxyl group in a molecule | numerator was obtained with the same processing method.
Moreover, the silica (3) which is an aminosilane processing filler, the silica (4) which is an epoxysilane processing filler, and the silica (5) which is a vinylsilane processing filler were obtained by the same processing method as described above.

8). Nonionic surfactant:
Polyglycerin condensed ricinoleic acid ester (manufactured by Taiyo Kagaku Co., Ltd., trade name “Tirabazole H-818”)

9. Maleimide:
・ Polyphenylmethanemaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name “BMI-2300”)

[Example 1]:
2.00 g of synthetic hectorite “Lucentite STN” and 84.53 g of DMF were mixed and stirred at room temperature until a completely uniform solution was obtained. Thereafter, 1.00 g of imidazole “2MAOK-PW” was added and stirred at room temperature until a completely homogeneous solution was obtained. Next, 25.00 g of silica “1-Fx” surface-treated with imidazole silane “IM-1000” was added and stirred at room temperature until a completely uniform solution was obtained.
Next, 53.29 g of biphenyl type epoxy resin “NC-3000H” was added and stirred at room temperature until a completely uniform solution was obtained. Next, 46.71 g of an epoxy resin curing agent “MEH7851-4H” made of a hydrophobic phenol compound was added to the above solution, and stirred at room temperature until a completely uniform solution was obtained to prepare a resin composition solution.
In order to evaluate the temporal stability, the resin composition solution was stored at 23 ° C. for 1 day (24 hours), and the subsequent fluidity (degree of gelation) was visually confirmed. A sample having fluidity equivalent to that after adjustment was marked with ◯, and a sample with clearly lower fluidity than that after adjustment was marked with ×.

  The resin composition solution obtained above was dried using an applicator on a transparent polyethylene terephthalate (PET) film (trade name “PET5011 550”, thickness 50 μm, manufactured by Lintec Co., Ltd.) subjected to a release treatment. The coating was applied to a thickness of 50 μm and dried in a gear oven at 100 ° C. for 12 minutes to prepare an uncured resin sheet of 200 mm × 200 mm × 50 μm. Next, the uncured product of the resin sheet was heated in a gear oven at 170 ° C. for 1 hour to prepare a semi-cured product of the resin sheet.

[Examples 2 to 19 and Comparative Examples 1 to 13]
A resin composition solution was prepared in the same manner as in Example 1 except that the resin composition solution had the composition shown in Tables 1 to 3, and an uncured product and a semicured product of the resin sheet were prepared. .

[Example 20]
The resin composition solution was prepared in the same manner as in Example 1 except that the resin composition solution had the composition shown in Table 2 and the stability over time of the resin composition solution was confirmed by the fluidity after 1 hour. Were prepared to prepare uncured and semi-cured resin sheets.

[Examples 21 to 30 and Comparative Example 14]
A resin composition solution was prepared in the same manner as in Example 1 except that the resin composition solution was formulated as shown in Table 4, and uncured and semi-cured products of the resin sheet were prepared.

(Copper plating treatment using uncured material in Examples 1 to 30 and Comparative Examples 1 to 14):
After the uncured product of each resin sheet obtained as described above was vacuum laminated on a glass epoxy substrate (FR-4, product number “CS-3665”, manufactured by Risho Kogyo Co., Ltd.) and cured at 170 ° C. for 30 minutes. The surface was subjected to the following (a) swelling treatment, then (b) permanganate treatment, that is, roughening treatment, and (c) copper plating treatment.

(A) Swelling treatment:
A resin sheet that was vacuum-laminated on a glass epoxy substrate was placed in an 80 ° C. swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan Co., Ltd.), and subjected to a rocking treatment for 10 minutes. Thereafter, it was thoroughly washed with pure water.

(B) Permanganate treatment:
A resin sheet vacuum-laminated on a glass epoxy substrate was placed in a roughened aqueous solution of potassium permanganate (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.) at 80 ° C. and rocked for 20 minutes. Further, the resin sheet that had been subjected to the permanganate roughening treatment was treated for 2 minutes using a 25 ° C. cleaning solution (Reduction Securigant P, manufactured by Atotech Japan Co., Ltd.) and then washed purely and thoroughly.

(C) Copper plating treatment:
Next, the electroless copper plating and the electrolytic copper plating treatment were performed on the resin sheet vacuum-laminated on the glass epoxy substrate and subjected to the roughening treatment according to the following procedure.
The resin sheet was treated with an alkaline cleaner (cleaner securigant 902) at 60 ° C. for 5 minutes to degrease and clean the surface. After washing, the resin sheet vacuum-laminated on the glass epoxy substrate was treated with a pre-dip solution (pre-dip neogant B) at 25 ° C. for 2 minutes. Thereafter, the resin sheet vacuum-laminated on the glass epoxy substrate was treated with an activator solution (activator neogant 834) at 40 ° C. for 5 minutes to attach a palladium catalyst. Next, it was treated for 5 minutes with a reducing solution (reducer Neogant WA) at 30 ° C.

  Next, the resin sheet vacuum-laminated on the glass epoxy substrate is placed in a chemical copper solution (basic print Gantt MSK-DK, copper print Gantt MSK, stabilizer print Gantt MSK), and electroless plating is performed with a plating thickness of about 0.5 μm. It was carried out until. After electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes to remove residual hydrogen gas. In all the processes up to the electroless plating process, each process was performed while the treatment liquid was 1 L on a beaker scale and the resin sheet was swung.

Next, electrolytic plating was carried out on the resin sheet vacuum-laminated on the glass epoxy substrate and subjected to the electroless plating treatment until the plating thickness became 25 μm. Copper sulfate (reducer Cu) was used as the electrolytic copper plating, and the current was 0.6 A / cm ² . After the copper plating treatment, heat curing was performed at 180 ° C. for 1 hour.

(Creating a cured product):
Furthermore, the semi-cured products obtained in Examples 1 to 30 and Comparative Examples 1 to 14 were heated under the curing conditions shown in Tables 1 to 4 to obtain cured bodies.

(Evaluation of resin compositions of Examples and Comparative Examples):
The semi-cured product of the resin sheets obtained in Examples 1 to 30 and Comparative Examples 1 to 14 and the performance of the cured body of the resin sheet and the surface state after the roughening treatment were evaluated by the following methods.

  Evaluation items are: Dielectric constant, 2. 2. dissipation factor, 3. Average linear expansion coefficient 4. Glass transition temperature (Tg), Breaking strength, 6. 6. Elongation at break, Roughening adhesive strength, 8. 8. Surface roughness (Ra, Rz), The copper bond strength was used. Moreover, about hardened | cured material, 1. Dielectric constant, 2. 2. dissipation factor, 3. Average linear expansion coefficient Glass transition temperature, 5. Breaking strength, 6. The elongation at break was evaluated. Moreover, in the process which performed the (a) swelling process about the said copper plating process, the roughening process by (b) permanganate process, and the (c) copper plating process, the uncured material was vacuum-laminated on the glass epoxy board | substrate. After the product is cured by heating to a semi-cured state, it is swollen and roughened. After evaluating the surface roughness and further copper plating, 7. 8. Roughened adhesive strength and Copper bond strength was measured. Details are as follows.

(Details of evaluation items and evaluation methods):
1. Dielectric constant, and 2. Dissipation factor:
A cured resin sheet is cut into 15 mm × 15 mm and 8 sheets are stacked to form a 400 μm-thick laminate, using a dielectric constant measuring device (product number “HP4291B”, manufactured by HEWLETT PACKARD) at room temperature. The dielectric constant and dielectric loss tangent at 1 GHz were measured.

3. Average linear expansion coefficient:
The cured body of the resin sheet is cut into 3 mm × 25 mm, and using a linear expansion coefficient meter (product number “TMA / SS120C”, manufactured by Seiko Instruments Inc.), the tensile load is 2.94 × 10 ⁻² N, the heating rate is 5 The average linear expansion coefficient (α1) of the cured product at 23 to 100 ° C. and the average linear expansion coefficient (α2) of the cured product at 150 to 260 ° C. were measured under the conditions of ° C./minute.

4). Glass transition temperature (Tg):
The cured body of the resin sheet is cut into 5 mm × 3 mm, and the temperature rising rate is 5 ° C./min using a viscoelastic spectrorometer (product number “RSA-II”, manufactured by Rheometric Scientific F.E.). Under the conditions, measurement was performed up to 30 to 250 ° C., and the temperature at which the loss rate tan δ became the maximum value (glass transition temperature Tg) was measured.

5. Breaking strength, and 6. Elongation at break:
A cured resin sheet (thickness: 100 μm) is cut to 10 × 80 mm, and using a tensile tester (trade name “Tensilon”, manufactured by Orientec Co., Ltd.) under conditions of a distance between chucks of 60 mm and a crosshead speed of 5 mm / min. A tensile test was performed to measure the breaking strength (MPa) and the breaking elongation (%).

7). Roughening adhesive strength:
A glass epoxy substrate (FR-4, product number “CS-3665”, manufactured by Risho Kogyo Co., Ltd.) is vacuum-laminated with an uncured resin sheet, and after heat treatment at 170 ° C. for 30 minutes, the above swelling treatment and permanganate Roughening treatment, chemical copper plating and electrolytic copper plating, heat-cured at 180 ° C. for 1 hour, cut into a 10 mm width on the surface of the copper plating layer, a tensile tester (trade name “Autograph”, Using Shimadzu Corporation), the measurement was performed under the condition of a crosshead speed of 5 mm / min, and the roughened adhesive strength was measured.

8). Surface roughness (Ra, Rz):
A semi-cured sheet is vacuum laminated on a glass epoxy substrate (FR-4, product number “CS-3665”, manufactured by Risho Kogyo Co., Ltd.), heat-treated at 170 ° C. for 30 minutes, and then subjected to the swelling treatment and roughening with permanganate. The treatment was performed. The surface roughness (Ra, Rz) in the measurement range of 100 μm ² was measured on the resin surface with a scanning laser microscope (product number “1LM21”, manufactured by Lasertec Corporation).

9. Copper bond strength:
A semi-cured product of a resin sheet was laminated in a vacuum on a CZ-treated copper foil (CZ-8301, manufactured by MEC), and heat-treated at 180 ° C. for 1 hour. Cut the surface of the copper foil to 10mm width and measure it using a tensile tester (trade name "Autograph", manufactured by Shimadzu Corporation) under the condition of a crosshead speed of 5mm / min. It was measured.

  Said evaluation result is shown to following Tables 1-4 with a resin composition composition.

As is clear from the evaluation results of Tables 1 to 4, in Comparative Examples 1 to 8 using a resin composition not containing the nonionic surfactant (d), for example, Examples 1 to 4 and Comparative Examples 1 to 4 are used. In comparison with the above, the copper bond strength or the roughened bond strength is low, or the surface roughness after the roughening treatment is large. Further, even in Comparative Examples 9 to 12 using a resin composition that contains a nonionic surfactant (d) but does not fall within the specific range defined in the present invention, for example, between Example 13 and Comparative Example 9 From the comparison or the comparison between Example 15 and Comparative Example 12, the copper bond strength and the roughened bond strength are low, or the surface roughness after the roughening treatment is large. Furthermore, in Comparative Example 14 using a resin composition containing silica that has not been treated with imidazole silane, aminosilane, or epoxy silane but has been treated with vinyl silane, the copper bond strength and the roughened bond strength are low.
On the other hand, the epoxy resin (a), the curing agent (b), the silica (c) having a specific diameter treated with imidazole silane, aminosilane or epoxy silane, and the nonionic surfactant (d) of the present invention at a specific ratio. In Examples 1-30 using the contained resin composition, it is clear that the surface roughness after the roughening treatment is small and the copper adhesive strength and the roughening adhesive strength are high. In Examples 29 and 30 using the resin composition containing the maleide compound (f), it can be seen that the glass transition temperature (Tg) is particularly high and the linear expansion coefficient is low.
Furthermore, in the comparison between Example 4 and Example 20 and Example 20 and Comparative Example 13, the system using imidazole silane-treated silica having no hydroxyl group is more than the system using imidazole silane-treated silica having a hydroxyl group. It is clear that the storage stability is excellent.

  In particular, the epoxy resin composition of the present invention comprises 25 to 400 parts by weight of silica (c) with respect to 100 parts by weight of the mixture (a + b) of the epoxy resin (a) and the epoxy resin curing agent (b). The nonionic surfactant (d) is contained in a proportion of 0.1 to 10 parts by weight, so that even when the silica content is high, good dispersibility can be maintained. The surface roughness of the cured product can be reduced, and a cured product excellent in copper plating adhesion can be obtained. For example, a substrate material, a sheet, or the like that forms a core layer or a build-up layer of a multilayer substrate It can be suitably used for laminates, copper foils with resin, copper-clad laminates, TAB tapes, printed circuit boards, prepregs, varnishes, and the like.

JP-A-9-168771 JP 2001-187836 A Japanese Patent Laid-Open No. 2002-128772 International Publication WO2007 / 032424

Claims (16)

Epoxy resin (a), epoxy resin curing agent (b), silica (c) treated with any one or more of imidazole silane, aminosilane, and epoxy silane, and having an average particle size of 5 μm or less, A resin composition containing a nonionic surfactant (d),
25 to 400 parts by weight of silica (c) and 0.1% of nonionic surfactant (d) are added to 100 parts by weight of the mixture (a + b) of the epoxy resin (a) and the epoxy resin curing agent (b). An epoxy resin composition comprising 1 to 10 parts by weight.   The nonionic surfactant (d) is at least one selected from the group consisting of an ester surfactant, an ether surfactant, and an ester / ether surfactant. The epoxy resin composition described.   Silica (c) treated with any one or more of imidazole silane, amino silane or epoxy silane has a treatment amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of silica. The epoxy resin composition according to claim 1 or 2.   The epoxy resin composition according to any one of claims 1 to 3, wherein the imidazole silane has no hydroxyl group in the molecule.   The epoxy resin (a) is at least selected from the group consisting of an epoxy resin having an anthracene skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an adamantane skeleton, an epoxy resin having a triazine skeleton, and an epoxy resin having a biphenyl skeleton. One type is contained 5 mass% or more with respect to the epoxy resin whole quantity, The epoxy resin composition of any one of Claims 1-4 characterized by the above-mentioned.   The epoxy resin curing agent (b) is selected from the group consisting of a curing agent having a biphenyl skeleton, an active ester curing agent, a curing agent having a benzoxazine structure, a curing agent having an aminotriazine skeleton, and a curing agent having a naphthalene skeleton. The epoxy resin composition according to claim 1, wherein at least one selected is contained in an amount of 5% by mass or more based on the total amount of the epoxy resin curing agent.   The epoxy resin composition according to claim 1, wherein the silica (c) has an average particle diameter of 1 μm or less.   The organic layered silicate (e) having an average particle diameter of 500 nm or less is 2 parts by weight or less with respect to 100 parts by weight of the mixture (a + b) of the epoxy resin (a) and the epoxy resin curing agent (b). The epoxy resin composition according to any one of claims 1 to 7, further comprising a proportion.   Furthermore, 2-45 mass% of maleimide type compounds (f) are contained with respect to the resin composition whole quantity, The epoxy resin composition of any one of Claims 1-8 characterized by the above-mentioned.   A prepreg obtained by impregnating a porous substrate with the epoxy resin composition according to any one of claims 1 to 9. A cured product obtained by subjecting the epoxy resin composition according to any one of claims 1 to 9 or a cured resin obtained by heat-curing the prepreg according to claim 10 to a roughening treatment,
A cured product having a surface roughness Ra of 0.2 μm or less and a surface roughness Rz of 2.0 μm or less.   The cured body according to claim 11, wherein a swelling treatment is performed before the resin cured product is roughened.   A sheet-like molding comprising the epoxy resin composition according to any one of claims 1 to 9, the prepreg according to claim 10, or the cured body according to claim 11 or 12. body.   A laminate comprising: a metal layer and / or an adhesive layer having adhesiveness formed on at least one surface of the sheet-like molded body according to claim 13.   The laminate according to claim 14, wherein the metal layer is formed as a circuit.   A multilayer laminate comprising at least one laminate selected from the laminates according to claim 14 or 15.