JP2005206831A - Thermosetting resin composition, resin sheet, and resin sheet for insulated substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermosetting resin composition which can give molding items such as a resin sheet having both excellent dynamic physical properties and excellent electrical properties that can respond to make an IC package high-frequency formation, and even if the case that it received a heat history exposed to an elevated temperature, causing a small dimensional change before and after the heat history, that is, showing a small linear expansion degree, and to prepare the resin sheet using the composition and a resin sheet for an insulated substrate. <P>SOLUTION: The thermosetting resin composition comprises, per 100 pts.wt. of an epoxy resin, 0.5-100 pts.wt. of an engineering plastic, 0.1-100 pts.wt. of a phyllosilicate, and an epoxy resin curing agent, and upon making the molding items, the engineering plastic exists as a dispersed phase. The former resin sheet comprises the composition. The latter resin sheet for the insulated substrate comprises the former resin sheet. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermosetting resin composition containing an epoxy resin as a main component, a resin sheet using the thermosetting resin composition, and a resin sheet for an insulating substrate using the resin sheet.

  In recent years, electronic devices have been rapidly improved in performance, functionality, and miniaturization, and electronic components used in electronic devices are also strongly required to be smaller and lighter. For this reason, there is a strong demand for further improvements in various performances such as heat resistance, mechanical strength, and electrical characteristics of materials constituting electronic components.

  A multilayer printed circuit board used in an electronic apparatus has a plurality of insulating substrates and a circuit pattern disposed between these insulating substrates. Conventionally, as this type of insulating substrate, that is, an interlayer insulating substrate (interlayer insulating layer), for example, a thermosetting resin prepreg obtained by impregnating a glass cloth with a thermosetting resin, a thermosetting resin or light A resin sheet made of a curable resin is used.

  Also in the multilayer printed board, it is desired that the interlayer be extremely thin in order to achieve high density and thinning. Therefore, as a material constituting the interlayer insulating substrate, an interlayer insulating substrate using a thin glass cloth or an interlayer insulating substrate not using a glass cloth is required.

  As an interlayer insulating substrate that satisfies the above requirements, for example, a thermosetting resin material modified with rubber (elastomer) or acrylic resin, a thermoplastic resin material or a thermosetting resin containing a large amount of an inorganic filler. What consists of materials etc. is known.

As a material comprising a thermosetting resin material containing a large amount of an inorganic filler, for example, a weight average molecular weight obtained by polymerizing a bifunctional epoxy resin and a bifunctional phenol in a solvent in the presence of a catalyst is 50,000. A non-fibrous inorganic filler having an average particle size of 0.8 to 5 μm is blended in the varnish mainly composed of the above high molecular weight epoxy polymer, polyfunctional epoxy resin, curing agent and cross-linking agent. A method for producing a multilayer printed wiring board (multilayer printed circuit board) is disclosed in which an epoxy adhesive film obtained by applying to one side or both sides and removing the solvent is used as an interlayer insulating layer.
JP 2000-183539 A

  In the multilayer printed circuit board by the above manufacturing method, by ensuring the area of the interface between the high molecular weight epoxy polymer or the polyfunctional epoxy resin and the inorganic filler is sufficient, mechanical properties such as mechanical strength are secured, An attempt is made to reduce the linear expansion coefficient (thermal linear expansion coefficient). However, the interlayer insulating layer constituting the multilayer printed board contains a large amount of inorganic filler in order to satisfy the required physical properties, so that the moldability and the suitability of the manufacturing process are often impaired. There is a problem that it is difficult to reduce the thickness of the insulating layer. In addition, since the interlayer insulating layer constituting the multilayer printed circuit board contains a large amount of inorganic filler, the obtained multilayer printed circuit board is often opaque, and the surface and the back surface of the multilayer printed circuit board are formed by a laser or the like. There is also a problem that it is difficult to perform the alignment.

On the other hand, an interlayer insulating substrate using a thin glass cloth or an interlayer insulating substrate not using a glass cloth has a problem that heat resistance and dimensional stability are insufficient. In addition, these interlayer insulating substrates are fragile and easily cracked, so that defective products tend to occur in the manufacturing process. Also,
Even in an interlayer insulating substrate using a thin glass cloth, since the glass cloth easily makes the substrate opaque, there is a problem that it is difficult to align the front and back surfaces of the multilayer printed board with a laser or the like.

  By the way, in the manufacture of multilayer printed circuit boards, the build-up method for obtaining a multilayer laminate by repeating the formation of a plurality of interlayer insulation layers and the formation of a circuit pattern on each insulation layer, or an insulation substrate on which circuit patterns are formed However, in any of the above manufacturing methods, the number of processes is large, so the quality of the material greatly affects the product yield.

In addition, because it includes each process such as plating process, curing process, and solder reflow process, the material constituting the multilayer printed circuit board has excellent performance such as solvent resistance, water resistance, heat resistance, and dimensional stability at high temperature. There is a strong demand for that. More specifically, for example, having resistance to acids, alkalis, and organic solvents, low hygroscopicity that tends to affect electrical characteristics, and affecting high-precision circuit connection between upper and lower insulating substrates Copper migration that tends to affect the reliability of electrical connection, that the dimensional change before and after heating is small, that it has heat resistance up to 260 ° C that is necessary for mounting with lead-free solder There is a strong demand for things that do not occur easily.
For example, multilayer boards for IC packages and multilayer printed boards obtained by the build-up method may be exposed to high temperatures due to heat generated by ICs during actual use. It is necessary to be able to maintain reliability. However, when the dimensional change of the resin at a high temperature is large, there is a problem that a metal wiring such as copper constituting the circuit and the resin are peeled off to cause a short circuit or disconnection.

  Moreover, even in a thin flexible multilayer substrate having flexibility that has been widely used in recent years, an adhesive layer that bonds single-layer flexible substrates to each other, a polyimide resin film that constitutes a flexible substrate, a copper that constitutes a circuit, etc. When the difference in thermal dimensional change (linear expansion coefficient) with the metal wiring is large, the same problem as described above tends to occur.

  In the multilayer printed circuit board according to the manufacturing method disclosed in Patent Document 1, high-temperature physical properties are improved by using an epoxy resin having excellent heat resistance and an inorganic filler in combination. Almost no improvement in physical properties is observed at a temperature higher than the transition temperature, and the improvement in physical properties is small even at temperatures lower than the glass transition temperature of the cured epoxy resin, and the hygroscopicity and solvent resistance are hardly improved.

  Conventionally, as a method for reducing the linear expansion coefficient at a temperature lower than the glass transition temperature of a cured resin, a method of blending an inorganic filler into a resin as described in Patent Document 1 is known. In order to reduce the difference in coefficient of linear expansion between the layer and the metal wiring, it is necessary to add a large amount of an inorganic filler. Moreover, even if a large amount of inorganic filler is blended, it is difficult to sufficiently reduce the linear expansion coefficient during high-temperature treatment such as during solder reflow that is exposed to a temperature higher than the glass transition temperature of the cured resin. Furthermore, in recent years, lead-free solder has been used in consideration of the environment, and the temperature of the solder reflow process has been further increased. Therefore, simply using a resin with excellent heat resistance, if the linear expansion coefficient is large at a temperature equal to or higher than the glass transition temperature of the cured resin, it tends to cause problems during high temperature processing such as solder reflow. There is.

Furthermore, in recent years, higher frequencies have been developed as part of higher functionality of IC packages, and the package material is required to have excellent dielectric properties such as low dielectric constant and low dielectric loss tangent. As for low dielectric constant and low dielectric loss tangent, improvement by resin, improvement by blending of inorganic filler, etc. are known. However, if low dielectric constant or low dielectric loss tangent is achieved by such a method, machine The mechanical properties such as the mechanical strength are lowered, and it is difficult to achieve both the mechanical properties and the electrical characteristics.

  As described above, the insulating substrate that constitutes a multilayer printed circuit board has excellent mechanical properties such as mechanical strength and electrical characteristics such as dielectric properties, and is also used during high-temperature processing such as solder reflow and actual use. There is a strong demand for a small dimensional change over time, that is, a low coefficient of linear expansion.

  In view of the above problems and the present situation, the object of the present invention is to combine excellent mechanical properties and excellent electrical characteristics that can cope with high frequency of IC packages, and to receive a thermal history exposed to high temperatures. Even if it is a case, the thermosetting resin composition which can obtain molded objects, such as a resin sheet etc. with small dimensional change before and behind a heat history, ie, a low coefficient of linear expansion, and this thermosetting resin composition The object is to provide a resin sheet using an object and a resin sheet for an insulating substrate.

  The thermosetting resin composition according to the invention according to claim 1 (the present invention) is 0.5 to 100 parts by weight of engineering plastics, 0.1 to 100 parts by weight of layered silicate, and 100 parts by weight of epoxy resin. An epoxy resin curing agent is contained, and engineering plastics exist as a dispersed phase when formed into a molded body.

  In a specific aspect of the thermosetting resin composition according to the present invention, 1 to 40 parts by weight of engineering plastics is contained with respect to 100 parts by weight of the epoxy resin.

  In still another specific aspect of the thermosetting resin composition according to the present invention, the engineering plastics is at least one kind selected from the group consisting of a polysulfone resin, a polyethersulfone resin, a polyimide resin, and a polyetherimide resin. It is an engineering plastic.

  In still another specific aspect of the thermosetting resin composition according to the present invention, the layered silicate is not present in the engineering plastics present as the dispersed phase.

  In still another specific aspect of the thermosetting resin composition according to the present invention, the layered silicate is at least one layered silicate selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite. It is characterized by that.

  In a limited aspect of the thermosetting resin composition according to the present invention, the layered silicate is selected from the group consisting of alkyl ammonium salts having 6 or more carbon atoms, aromatic quaternary ammonium salts, and heterocyclic quaternary ammonium salts. It contains at least one kind of ammonium salt.

In a further limited aspect of the thermosetting resin composition according to the present invention, part or all of the layered silicate has an average interlayer distance of (001) plane measured by wide angle X-ray diffraction method of 3 nm or more. The resin sheet according to the present invention is characterized by comprising a thermosetting resin composition configured according to the present invention.

  The resin sheet which concerns on this invention is obtained by hardening the thermosetting resin composition comprised according to this invention, It is characterized by the above-mentioned.

A resin sheet for an insulating substrate according to the invention described in claim 10 (the present invention) comprises the resin sheet according to claim 8 or 9.
Hereinafter, the present invention will be described in detail.

  The thermosetting resin composition of the present invention contains 0.5 to 100 parts by weight of engineering plastics, 0.1 to 100 parts by weight of layered silicate, and an epoxy resin curing agent with respect to 100 parts by weight of epoxy resin. .

  The epoxy resin used in the thermosetting resin composition of the present invention is an organic compound having at least one epoxy group in the molecule. The number of epoxy groups in the epoxy resin is preferably 1 or more per molecule, more preferably 2 or more. Here, the number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin.

  As said epoxy resin, conventionally well-known various epoxy resins may be sufficient and it is not specifically limited, For example, the following epoxy resin (1)-epoxy resin (11) etc. are mentioned. These epoxy resins may be used independently and 2 or more types may be used together.

  Examples of the epoxy resin (1) include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and bisphenol S type epoxy resins, phenol novolac type epoxy resins, and cresol novolak type epoxy resins. Novolak type epoxy resins such as resins, trisphenol methane triglycidyl ether, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, and aromatic epoxy resins such as naphthalene type epoxy resins and their hydrogenated products such as brominated products And halides.

  Examples of the epoxy resin (2) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxyl. Bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl) And alicyclic epoxy resins such as -5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane and bis (2,3-epoxycyclopentyl) ether. As a commercial item of 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) include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether. Fats such as glycidyl ether, diglycidyl ether of polypropylene glycol, polyglycidyl ether of long-chain polyols containing polyoxyalkylene glycol containing 2 to 9, preferably 2 to 4 alkylene groups, polytetramethylene ether glycol, etc. Group epoxy resins and the like.

Examples of the epoxy resin (4) include diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, and glycidyl dimer acid. Examples thereof include glycidyl ester type epoxy resins such as esters and hydrogenated products thereof.

  Examples of the epoxy resin (5) include triglycidyl isocyanurate, N, N′-diglycidyl derivative of cyclic alkylene urea, N, N, O-triglycidyl derivative of p-aminophenol, and N, N of m-aminophenol. , Glycidylamine epoxy resins such as O-triglycidyl derivatives and hydrogenated products thereof.

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

  Examples of the epoxy resin (7) include those obtained by epoxidizing unsaturated carbon double bonds in a polymer mainly composed of a conjugated diene compound or a partially hydrogenated product thereof, such as epoxidized polybutadiene. .

  Examples of the epoxy resin (8) include a polymer block mainly composed of a vinyl aromatic compound such as an epoxidized styrene-butadiene-styrene block copolymer (epoxidized SBS) and a conjugated diene compound or a partial hydrogen thereof. Examples thereof include epoxidized unsaturated carbon double bonds of a conjugated diene compound or a partially hydrogenated product thereof in a block copolymer having a polymer block mainly composed of an additive in the same molecule.

  Examples of the epoxy resin (9) include a polyester resin having one or more, preferably two or more epoxy groups per molecule.

  Examples of the epoxy resin (10) include a urethane-modified epoxy resin or a polycaprolactone-modified epoxy resin in which a urethane bond or a polycaprolactone bond is introduced into the structure of the epoxy resin (1) to the epoxy resin (9).

  Examples of the epoxy resin (11) include, for example, the above-described epoxy resin (1) to epoxy resin (10), acrylonitrile-butadiene copolymer rubber (NBR), terminal carboxyl group-modified butadiene-acrylonitrile copolymer rubber (CTBN), polybutadiene, and acrylic. Examples thereof include a rubber-modified epoxy resin containing a rubber component such as rubber.

  An oligomer or polymer having at least one oxirane ring in the molecule may be added to the epoxy resin.

  When the epoxy resin contains at least one selected from the group consisting of a bisphenol type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, and a naphthalene type epoxy resin, the molecular chain is rigid Therefore, the strength of the material and the dimensional stability at high temperature are excellent. Further, since the packing property of the molecule is high, the electrical characteristics such as dielectric loss tangent are also excellent.

The epoxy resin curing agent used in the thermosetting resin composition of the present invention may be any conventionally known epoxy resin curing agent, and is not particularly limited. For example, the epoxy resin curing agent is synthesized from an amine compound or an amine compound. For example, compounds such as polyaminoamide compounds, tertiary amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization catalysts, dicyandiamide and derivatives thereof It is done. These epoxy resin curing agents may be used alone or in combination of two or more.

  Examples of amine compounds include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, and derivatives thereof, mensendiamine, isophoronediamine, bis ( 4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa Cycloaliphatic amines such as spiro (5,5) undecane and derivatives thereof, m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodi Enirusurufon, alpha, alpha-bis (4-aminophenyl)-p-like aromatic amines and their derivatives, such as diisopropyl benzene.

  Examples of the compound synthesized from the amine compound include the above amine compound and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid, hexahydroisophthalic acid. Polyaminoamide compounds and derivatives thereof synthesized from carboxylic acid compounds such as the above, polyaminoimide compounds synthesized from the above amine compounds and maleimide compounds such as diaminodiphenylmethane bismaleimide, and derivatives thereof, synthesized from the above amine compounds and ketone compounds Ketimine compounds and derivatives thereof, polyamino compounds synthesized from the above amine compounds and epoxy compounds, urea, thiourea, aldehyde compounds, phenol compounds, acrylic compounds, and the like Derivatives thereof.

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 and derivatives thereof.
Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and derivatives thereof.

  Examples of the hydrazide compound include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosanedioic acid dihydrazide, adipic acid dihydrazide, and these And the like.

  Examples of the melamine compound include 2,4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof.

  Examples of acid anhydrides include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2,5-dioxotetrahydro Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazelinic anhydride, polydodecanedioic anhydride, Chlorendic anhydride And derivatives thereof.

As the phenol compound, any compound having a phenol structure may be used. For example, a hydrophobic phenol compound represented by the following general formulas (1) to (3), phenol novolak, o-cresol novolak, p-cresol novolak, t -Butylphenol novolak, dicyclopentadiene cresol and derivatives thereof.

In the general 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 the general formula (2), n represents 0 or an integer of 1 to 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 number of 1 to 2.
0 represents a carbon atom-containing molecular chain group, p and q each represent an integer of 1 to 6, and r represents an integer of 1 to 11.

In the above formula (3), R ⁶ represents hydrogen or a molecular chain group containing 1 to 20 carbon atoms. Examples of the carbon atom-containing molecular chain group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, and a propyl group, or a group having an alicyclic hydrocarbon such as benzene, naphthalene, and cyclopentadiene.

  When the epoxy resin curing agent is the above-mentioned phenol compound, the thermosetting resin composition and the cured product of the molded body made of this thermosetting resin composition are dimensional stability when given heat resistance and thermal history. Is improved and water absorption is reduced. In particular, when the epoxy resin curing agent is a hydrophobic phenol compound represented by the above general formulas (1) to (3), the thermosetting resin composition or the cured product of the molded body has heat resistance and thermal history. In addition to improving the dimensional stability and lowering the water absorption, the dielectric characteristics such as the low dielectric constant and the low dielectric loss tangent are also improved, and excellent electrical characteristics are exhibited.

  Examples of the heat latent cationic polymerization catalyst include ionic properties such as benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt, and benzylsulfonium salt using antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as a counter anion. Non-ionic thermal latent cationic polymerization catalyst such as thermal latent cationic polymerization catalyst, N-benzylphthalimide, and aromatic sulfonic acid ester.

  Examples of the photolatent cationic polymerization catalyst include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts using antimony hexafluoride, phosphorus hexafluoride, boron tetrafluoride and the like as counter anions, and the like. Ionic photolatent cationic polymerization catalysts such as organometallic complexes such as iron-allene complex, titanocene complex, arylsilanol-aluminum complex, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, Nonionic photolatent cationic polymerization catalysts such as N-hydroxyimide sulfonate and the like.

  The blending ratio of the epoxy resin curing agent to the epoxy resin is not particularly limited, but the epoxy group in the epoxy resin and the epoxy reactive functional group in the epoxy resin curing agent are equivalent to 1: 0. The blending ratio is preferably about 5 to 1: 2. When the above-mentioned equivalent ratio is a blending ratio that deviates from the range of about 1: 0.5 to 1: 2, the heat resistance of the thermosetting resin composition or the cured product of the molded body becomes insufficient, or the insulation property is low. May get worse.

  The engineering plastics used in the thermosetting resin composition of the present invention are high-performance plastics used in industrial applications (industrial applications), and generally have high strength and heat resistance, and are resistant to chemicals. It has advantages such as excellent properties.

  The engineering plastics are not particularly limited. For example, polysulfone resin, polyethersulfone resin, polyimide resin, polyetherimide resin, polyamide resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene. Examples include terephthalate resin, aromatic polyester resin, modified polyphenylene oxide resin, polyphenylene sulfide resin, and polyether ketone resin. Among them, considering the compatibility with epoxy resin and the characteristics of engineering plastics itself, polysulfone resin At least one engineering plastic selected from the group consisting of polyethersulfone resin, polyimide resin and polyetherimide resin It is preferably used. These engineering plastics may be used independently and 2 or more types may be used together.

  The engineering plastics exist as a dispersed phase when the thermosetting resin composition of the present invention is formed into a molded body.

  When engineering plastics exist as a dispersed phase when the thermosetting resin composition is formed into a molded body, the molded body made of the thermosetting resin composition and the cured product thereof have sufficient mechanical properties. , It exhibits excellent electrical characteristics. As a method of dispersing the engineering plastics, it is performed by appropriately adjusting the kind of solvent, the mixing method, and the like.

  When the thermosetting resin composition is formed into a molded body, the engineering plastics are preferably finely dispersed. More preferably, the engineering plastics are preferably uniformly dispersed in 3 μm or less. When engineering plastics are finely dispersed, the molded article made of a thermosetting resin composition and its cured product have excellent electrical characteristics such as improved resin strength and elongation, and improved fracture toughness. Expressed.

  Moreover, it is preferable that the layered silicate mentioned later does not exist in the engineering plastics existing as the dispersed phase. The absence of layered silicate in the engineering plastics present as the dispersed phase is considered to be absorbed by the engineering plastics present as the dispersed phase in the molded product made of the thermosetting resin composition and the stress applied to the cured product. Therefore, excellent toughness can be imparted without impairing the mechanical properties of the matrix layer. As a method for suppressing the invasion of layered silicate into engineering plastics, for example, there is a method of increasing the affinity for epoxy resin while lowering the affinity for engineering plastics by increasing the polarity of layered silicate. Can be mentioned.

  In the thermosetting resin composition of this invention, it is necessary for the said engineering plastics to contain 0.5-100 weight part with respect to 100 weight part of said epoxy resins. The engineering plastics is preferably contained in an amount of 1 to 40 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.

  When the content of engineering plastics relative to 100 parts by weight of the epoxy resin is less than 0.5 parts by weight, the above-mentioned effect due to the inclusion of engineering plastics cannot be obtained sufficiently, and conversely, the engineering plastics relative to 100 parts by weight of the epoxy resin. If the S content exceeds 100 parts by weight, the amount of engineering plastics becomes excessive, and the physical properties of the thermosetting resin composition and the cured product of the molded article are lowered.

  Further, if the content of engineering plastics relative to 100 parts by weight of epoxy resin is less than 1 part by weight, the effect of imparting toughness may be inferior. Conversely, the content of engineering plastics relative to 100 parts by weight of epoxy resin may be 40 If it exceeds the parts by weight, the viscosity becomes higher than necessary before curing, and the workability during lamination, such as unevenness followability, may deteriorate.

  The layered silicate used in the thermosetting resin composition of the present invention means a layered silicate compound having an exchangeable metal cation between crystal layers. This layered silicate may be a natural product or a synthetic product.

  The layered silicate is not particularly limited. For example, smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite, nontronite, and swelling mica (swelling mica) , Vermiculite, halloysite, and the like. Among them, at least one layered silicate selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite is preferably used. Among them, the dispersibility in the resin is good and the resin strength and the dimensional stability at high temperature can be improved. Therefore, at least one kind selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite. Layered silicates are preferably used, especially hectorite. These layered silicates may be used alone or in combination of two or more.

  The layered silicate is not particularly limited, but the average length is preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less. When the average length of the layered silicate is 2 μm or less, the transparency of the thermosetting resin composition or the molded body is improved, and the alignment with the lower substrate or the like can be facilitated during operation. Further, when the average length of the layered silicate is 1 μm or less, the residue of the thermosetting resin composition or the molded body hardly remains at the time of laser processing, and laser workability is improved. Furthermore, when the average length of the layered silicate is 0.5 μm or less, the thermosetting resin composition or the molded body can be used as an optical material or a material for an optical waveguide.

  The crystal shape of the layered silicate is not particularly limited, but the average length is preferably 0.01 μm or more, the thickness is 0.001 to 1 μm, and the aspect ratio is preferably 20 to 500. More preferably, the average length is 0.05 μm or more, the thickness is 0.01 to 0.5 μm, and the aspect ratio is 50 to 200.

  The layered silicate preferably has a large shape anisotropy defined by the following relational expression. By using the layered silicate having a large shape anisotropy, the thermosetting resin composition and the molded product exhibit more excellent mechanical properties such as mechanical strength.

Shape anisotropy = surface area of laminar crystal laminate surface / surface area of laminar crystal laminate side surface The exchangeable metal cation present between the layered silicate crystal layers is present on the lamellar crystal surface of the lamellar silicate It is a metal ion such as sodium ion or calcium ion, and these metal ions have cation exchange properties with other cationic substances, so various kinds of cationic substances are placed between the crystal layers of the layered silicate. Can be inserted (intercalated) or captured.

The cation exchange capacity of the layered silicate is not particularly limited, but is preferably 50 to 200 meq / 100 g. When the cation exchange capacity of the layered silicate is less than 50 meq / 100 g, the amount of the cationic substance inserted or trapped between the crystal layers of the layered silicate due to the cation exchange is reduced, so that the crystal layer is not sufficiently separated. If the cation exchange capacity of the layered silicate exceeds 200 meq / 100g, the bonding force between the crystal layers of the layered silicate becomes too strong and the crystal flakes peel off. May be difficult.

  It is preferable that the said layered silicate is what improved the dispersibility in an epoxy resin or an epoxy resin hardening | curing agent by giving a chemical treatment. Hereinafter, a layered silicate having improved dispersibility in an epoxy resin or an epoxy resin curing agent by performing a chemical treatment will be referred to as an “organized layered silicate”.

  Although the said chemical treatment is not specifically limited, For example, it can give by the chemical modification (1) method-chemical modification (6) method shown below. These chemical modification methods may be used alone or in combination of two or more.

  The chemical modification (1) method is also referred to as a cation exchange method using a cationic surfactant. Specifically, when the thermosetting resin composition of the present invention is obtained, the crystalline layer of the layered silicate is previously separated from the cationic interface. In this method, cation exchange is performed with an activator to make it nonpolar.

  The cationic surfactant is not particularly limited, and examples thereof include a quaternary ammonium salt, a quaternary phosphonium salt, and the like, and among them, the crystal layer of the layered silicate can be sufficiently nonpolarized. Therefore, at least one ammonium salt selected from the group consisting of alkyl ammonium salts having 6 or more carbon atoms, aromatic quaternary ammonium salts and heterocyclic quaternary ammonium salts is preferably used. These cationic surfactants may be used alone or in combination of two or more.

  The quaternary ammonium salt is not particularly limited, and examples thereof include trimethylalkylammonium salt, triethylalkylammonium salt, tributylalkylammonium salt, dimethyldialkylammonium salt, dibutyldialkylammonium salt, methylbenzyldialkylammonium salt, Alkylammonium salts such as dibenzyldialkylammonium salt, trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, benzylmethyl {2- [2- (p-1,1,3,3-tetramethyl) A quaternary ammonium salt (aromatic quaternary ammonium salt) having an aromatic ring such as butylphenoxy) ethoxy] ethyl} ammonium chloride, trimethylphenylammonium A quaternary ammonium salt derived from an aromatic amine (aromatic quaternary ammonium salt), an alkylpyridinium salt, an imidazolium salt and the like, a quaternary ammonium salt having a heterocyclic ring (heterocyclic quaternary ammonium salt), and 2 polyethylene glycol chains. Dialkyl quaternary ammonium salts having two polypropylene glycol chains, trialkyl quaternary ammonium salts having one polyethylene glycol chain, trialkyl quaternary ammonium salts having one polypropylene glycol chain, etc. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured beef tallow dimethyl ammonium salt, distearyl dibenze Ammonium salts, N- polyoxyethylene -N- lauryl -N, N- dimethyl ammonium salt is preferably used. These quaternary ammonium salts may be used alone or in combination of two or more.

The quaternary phosphonium salt is not particularly limited, and examples thereof include dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethyl. Examples thereof include phosphonium salts and distearyl dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.

  The chemical modification (2) method is a chemical affinity with a functional group or a hydroxyl group capable of chemically bonding a hydroxyl group present on the crystal surface of the organically modified layered silicate subjected to the chemical treatment by the chemical modification (1) method. This is a method of chemically treating with a compound having one or more functional groups having high properties at the molecular terminals.

  The chemical modification (3) method is a chemical affinity with a functional group or a hydroxyl group capable of chemically bonding a hydroxyl group present on the crystal surface of the organically modified layered silicate subjected to the chemical treatment by the chemical modification (1) method. This is a method of chemical treatment with a compound having one or more functional groups having high properties at one end of the molecule and one or more reactive functional groups at the other end of the molecule.

  The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxyl group, an epoxy group (glycidyl group), and a carboxyl group (dibasic). Acid anhydrides), hydroxyl groups, isocyanate groups, aldehyde groups, amino groups, and the like.

  The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited. Examples thereof include compounds, titanate compounds, epoxy compounds, carboxylic acids, alcohols, etc. Among them, silane compounds are preferably used. These compounds may be used independently and 2 or more types may be used together.

  Although it does not specifically limit as a silane compound used by the said chemical modification (2) method, For example, a methyltriethoxysilane, a dimethyldimethoxysilane, a trimethylmethoxysilane, a hexyltrimethoxysilane, a hexyltriethoxysilane, an octadecyl Examples include trimethoxysilane and octadecyltriethoxysilane. The silane compounds used in these chemical modification (2) methods may be used alone or in combination of two or more.

  In addition, the silane compound used in the chemical modification (3) method is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ-amino. Propyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethylethoxysilane, N-β- (Aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropylmethyl Dimethoxysilane, Examples include γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane. These silane compounds used in the chemical modification (3) method may be used alone or in combination of two or more.

  The chemical modification (4) method is a method in which the crystallized surface of the organically modified layered silicate subjected to the chemical treatment by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.

The compound having an anionic surface activity is not particularly limited as long as it can chemically treat the layered silicate by ionic interaction. For example, sodium laurate, sodium stearate, sodium oleate Higher alcohol sulfates, secondary higher alcohol sulfates, unsaturated alcohol sulfates, and the like. These compounds having anionic surface activity may be used alone or in combination of two or more.

  The chemical modification (5) method is a method in which a chemical treatment is performed with a compound having one or more reactive functional groups other than the anion site in the molecular chain among the compounds having anionic surface activity.

  The chemical modification (6) method includes an organically modified layered silicate that has been chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method, and further, for example, maleic anhydride-modified polyphenylene ether resin. It is the method of chemically processing with resin which has a functional group which can react with layered silicate like.

  In the thermosetting resin composition of the present invention, a part or all of the layered silicate (including the organically modified layered silicate) has an average interlayer distance of (001) plane measured by a wide angle X-ray diffraction method. It is preferably 3 nm or more and dispersed in a state where the number of laminations is 5 or less, more preferably the average interlayer distance is 3 to 5 nm and the number of laminations is 5 or less. It is that.

  In addition, the average interlayer distance of the layered silicate referred to in the present invention means an average distance between layers when the flaky crystal of the layered silicate is regarded as a layer, and can be calculated by a wide angle X-ray diffraction method. it can. Further, the ratio of the layered silicate dispersed as a laminate of 5 layers or less was observed by magnifying the thermosetting resin composition from 50,000 times to 100,000 times with a transmission electron microscope. The total number of layered silicate laminates (X) that can be observed and the number of layered silicate layers (Y) dispersed as a laminate of 5 layers or less can be measured and calculated by the following formula.

Ratio of layered silicate dispersed as a laminate of 5 layers or less (%) = (Y / X) × 100
When part or all of the layered silicate is dispersed in the thermosetting resin composition in a state where the average interlayer distance is 3 nm or more and the number of laminated layers is 5 layers or less, the epoxy resin or the epoxy resin is cured. The interface area between the agent and the layered silicate becomes sufficiently large, and the distance between the flaky crystals of the layered silicate becomes appropriate, and the high-temperature physical properties of the thermosetting resin composition and the cured product of the molded body, Mechanical properties, heat resistance, dimensional stability, etc. can be further improved. However, if part or all of the layered silicate is dispersed in the thermosetting resin composition with the average interlayer distance exceeding 5 nm, the layered silicate crystal flakes are separated for each layer and interacted with each other. Is so weak that it can be ignored, the binding strength (constraint strength) at high temperatures becomes weak, and the dimensional stability of the thermosetting resin composition or the cured product of the molded article may not be sufficiently improved.

  Specifically, part or all of the layered silicate is dispersed in the thermosetting resin composition in a state where the number of laminated layers is 5 or less. Specifically, the interaction between the flaky crystals of the layered silicate Means that part or all of the laminate of flaky crystals is dispersed, and preferably 10% or more of the laminate of layered silicate is dispersed in a state of 5 layers or less. More preferably, 20% or more of the layered silicate laminate is dispersed in a state of 5 layers or less.

  Further, the number of laminated layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and still more preferably, in order to sufficiently obtain the above-described effect due to the dispersion of the layered silicate. Is one layer.

In order to reduce the number of layers, for example, the amount of chemical treatment such as the amount of a cationic surfactant to be cation-exchanged is increased so that the dispersibility of the layered silicate is improved. However, in this case, the physical properties may be deteriorated due to a large amount of the cationic surfactant. In addition, it is mentioned that the dispersion conditions at the time of dispersion are made more severe. For example, when dispersing with an extruder, the shear force during extrusion is increased, or when stirring with a mixer, rotation of rotating blades is performed. Examples include increasing the number.

  However, in practice, if the layered silicate is dispersed in about three layers, the above-described effects can be sufficiently exerted. Therefore, it is preferred that 30% or more of the layered silicate laminate is dispersed in three or more layers. In addition, if the proportion of three or more layers is excessively increased, the above-described physical properties are difficult to obtain. Therefore, the proportion of the layered silicate laminate dispersed in three or more layers is 70% or less. preferable.

  In the thermosetting resin composition of the present invention, when the layered silicate is dispersed in the above state, the area of the interface between the epoxy resin or the epoxy resin curing agent and the layered silicate becomes sufficiently large. ing. Therefore, the interaction between the epoxy resin or the epoxy resin curing agent and the surface of the layered silicate is increased, the melt viscosity of the thermosetting resin composition is increased, the thermoformability by hot press and the like is improved, and the molding is performed. Shape retention when the body is shaped into a desired shape by embossing or embossing is also improved.

  In addition, mechanical properties such as elastic modulus are improved over a wide temperature range from room temperature to high temperature, and even at high temperatures above the glass transition temperature or the melting point of the cured product of thermosetting resin compositions and molded products. The physical properties are maintained, and the linear expansion coefficient at high temperatures can be kept low.

  In addition, when a low melting point epoxy resin is used as the epoxy resin, the low melting point epoxy resin alone exhibits fluidity at high temperatures and cannot be maintained in a sheet shape or the like. By dispersing it in the epoxy resin, it becomes possible to maintain a sheet-like shape even at high temperatures. Therefore, the thermosetting resin composition using the low melting point epoxy resin can be applied even in the manufacturing process having a high temperature process. This is because the layered silicate in a finely dispersed state acts as a kind of pseudo-crosslinking point even in a high temperature region above the glass transition temperature or above the melting point of the thermosetting resin composition, molded product or epoxy resin itself. This is probably due to this.

  In addition, since the distance between the lamellar crystals of the layered silicate becomes an appropriate size, the lamellar crystals of the lamellar silicate move during combustion, so that it becomes easy to form a sintered body that becomes a flame retardant coating. Since this sintered body is formed at an early stage during combustion, it can block the supply of oxygen from the outside and also block the combustible gas generated by the combustion. Therefore, the thermosetting resin composition and the cured product of the molded product exhibit excellent flame retardancy.

  Furthermore, in the thermosetting resin composition of the present invention, since the layered silicate is finely dispersed in a nanometer size, for example, on the substrate configured by curing the thermosetting resin composition of the present invention, When drilling is performed with a laser such as a carbon dioxide laser, resin components such as epoxy resins, epoxy resin curing agents, engineering plastics, and layered silicate components simultaneously decompose and evaporate, resulting in partially remaining layered silicate. Residues are only small with a size of several μm or less. Therefore, since the layered silicate residue remaining by the desmear process can be easily removed, it is possible to reliably suppress the occurrence of defective plating due to the residue generated by the drilling process.

  The method for dispersing the layered silicate in the epoxy resin or the epoxy resin curing agent is not particularly limited. For example, the method using the organic layered silicate, the method using the dispersant, the layered silicate. And a method of mixing with an epoxy resin or an epoxy resin curing agent in a state where is dispersed in a solvent. By using these dispersing methods, the layered silicate can be uniformly and finely dispersed in the epoxy resin or the epoxy resin curing agent.

  In the thermosetting resin composition of this invention, it is required that the said layered silicate 0.1-100 weight part contains with respect to 100 weight part of said epoxy resins.

  When the content of the layered silicate with respect to 100 parts by weight of the epoxy resin is less than 0.1 parts by weight, the above-mentioned effect due to the inclusion of the layered silicate cannot be sufficiently obtained, and conversely, the layered with respect to 100 parts by weight of the epoxy resin. If the content of silicate exceeds 100 parts by weight, the density of the thermosetting resin composition or the cured product of the molded body becomes too high, the mechanical properties are lowered, and the practicality is impaired. The layered silicate is preferably contained in the range of 0.2 to 40 parts by weight with respect to 100 parts by weight of the resin component containing the epoxy resin and the epoxy resin curing agent. The layered silicate is more preferably contained in the range of 0.5 to 20 parts by weight, and still more preferably contained in the range of 1.0 to 10 parts by weight. If the layered silicate is less than 0.2 parts by weight, the mechanical properties after curing may be lowered, and if the layered silicate is more than 40 parts by weight, the viscosity of the resin increases, for example, a thin sheet It becomes difficult to mold into a desired shape.

In addition, in the thermosetting resin composition containing no engineering plastics, when the layered silicate is dispersed, the linear expansion coefficient decreases. Furthermore, the elongation of the thermosetting resin composition is reduced, and is easily embrittled.
On the other hand, in the thermosetting resin composition containing engineering plastics, when the layered silicate is dispersed, it becomes difficult to become brittle, and excellent electrical characteristics are exhibited. Furthermore, when engineering plastics are contained, since the thermosetting resin composition has a high melting point, the reduction in the linear expansion coefficient is reduced.

  In addition to the epoxy resin, the epoxy resin curing agent, the engineering plastics and the layered silicate, which are essential components, the thermosetting resin composition of the present invention can be used together with, for example, an epoxy resin. A polymerizable resin may be contained.

  The resin copolymerizable with the epoxy 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, and examples thereof include resins obtained by modifying polyphenylene ether resins with functional groups having thermosetting properties such as epoxy groups, isocyanate groups, and amino groups. It is done. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more.

  The benzoxazine resin refers to a monomer capable of ring-opening polymerization of an oxazine ring of a benzoxazine monomer and a resin obtained by ring-opening polymerization. The benzoxazine monomer is not particularly limited. For example, a benzoxazine ring nitrogen having a substituent such as a phenyl group, a methyl group or a cyclohexyl group bonded thereto, or a phenyl group between two oxazine ring nitrogens. And those having a substituent such as a group, a methyl group or a cyclohexyl group bonded thereto. These benzoxazine monomers and benzoxazine resins may be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention may contain, for example, a thermoplastic elastomer (thermoplastic rubber), a crosslinked rubber, a thermoplastic resin such as a polyvinyl acetal resin, or the like, if necessary.

The thermoplastic elastomer is not particularly limited, and examples thereof include styrene elastomers, olefin elastomers, urethane elastomers, and polyester elastomers. These thermoplastic elastomers may be modified with a functional group such as an epoxy group, an isocyanate group, or an amino group in order to enhance the compatibility with the epoxy resin. Moreover, these thermoplastic elastomers may be used independently and 2 or more types may be used together.

  The crosslinked rubber is not particularly limited. For example, isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene copolymer rubber, nitrile rubber, butyl rubber, chloroprene rubber, ethylene-propylene copolymer rubber. Cross-linked bodies such as silicone rubber and urethane rubber. These cross-linked rubbers are modified with functional groups such as epoxy groups, isocyanate groups, amino groups such as cross-linked products of epoxy-modified butadiene rubbers and epoxy-modified nitrile rubbers in order to enhance compatibility with the epoxy resin. May be. Moreover, these crosslinked rubbers may be used independently and 2 or more types may be used together.

  In addition, the thermosetting resin composition of the present invention includes, for example, a filler other than the layered silicate, a softening agent (plasticizer), a nucleating agent, an antioxidant (anti-aging agent), a heat, if necessary. One kind or two or more kinds of various additives such as a stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, an antistatic agent, an antifogging agent, a colorant, and an organic solvent may be contained.

  The method for producing the thermosetting resin composition of the present invention is not particularly limited. For example, the epoxy resin, the epoxy resin curing agent, the engineering plastics, and the layered silicate which are essential components are used. A direct kneading method in which each predetermined amount and each predetermined amount of one or more other components to be contained as needed are directly blended and kneaded at room temperature or under heating, and each predetermined amount of the above essential components; Solution mixing method in which each predetermined amount of the above-mentioned other components is mixed in a solvent and then the solvent is removed, and a predetermined amount or more of layered silicic acid is added to an epoxy resin, an epoxy resin curing agent or engineering plastics or other resin in advance. Prepare a masterbatch that contains salt and knead it, and also add a predetermined amount of this masterbatch, an epoxy resin, and an epoxy resin curing agent. Alternatively, the predetermined amount of each of the engineering plastics or other resin and the predetermined amount of one or more other components to be included as necessary are directly blended at room temperature or under heating. Examples include a master batch method in which the solvent is removed after kneading or mixing in a solvent.

  Examples of the solvent include acetone, methyl ethyl ketone, hexane, cyclohexane, diisopropyl ether, xylene, 1-propanol, diethyl ether, toluene, tetrahydrofuran, dimethylformamide, chlorobenzene, benzene, 1,2-dichloroethane, and other aromatic hydrocarbons, ethers , Ketones, halogenated hydrocarbons and the like.

  In the above master batch method, epoxy resin, epoxy resin curing agent, engineering plastics or epoxy resin used when diluting master batches and master batches containing layered silicates to obtain a predetermined layered silicate concentration The master batch dilution resin composition containing an epoxy resin curing agent, engineering plastics, or other resin may have the same composition or a different composition.

  The kneading method of each component in the production method of the thermosetting resin composition of the present invention is not particularly limited, for example, using a conventionally known kneader such as an extruder, a two roll, a Banbury mixer, What is necessary is just to knead | mix each component uniformly, applying a shear force under normal temperature or a heating. By applying a shearing force during the kneading, the average length of the layered silicate may be further shortened.

  In the thermosetting resin composition of the present invention, the epoxy resin, the epoxy resin curing agent, and the engineering plastics and the layered silicate are used in combination. Glass transition temperature and heat distortion temperature rise. In particular, the electrical properties and toughness can be further improved without impairing the mechanical properties of the cured product by not causing the layered silicate to exist in the engineering plastics that exist as a dispersed phase when formed into a molded body. . Therefore, it is possible to obtain a molded body such as a resin sheet that has a low coefficient of linear expansion at a high temperature and is excellent in heat resistance, mechanical characteristics, dielectric characteristics, and the like.

  In general, gas molecules are much more easily diffused in the resin than inorganic fillers such as layered silicates. Even in the thermosetting resin composition of the present invention, gas molecules diffuse while bypassing the layered silicate when diffusing in the epoxy resin, the epoxy resin curing agent and the engineering plastics, so that the gas barrier property is also improved. A molded body can be obtained. Similarly, barrier properties against other than gas molecules can be improved, and solvent resistance can be improved, and hygroscopicity and water absorption can be reduced. Therefore, for example, a cured product of a resin sheet made of the thermosetting resin composition of the present invention can be suitably used as an interlayer insulating substrate in a multilayer printed circuit board, and copper migration from a circuit made of copper is suppressed. You can also Furthermore, it is possible to suppress the occurrence of defects such as defective plating due to bleeding out of the surface of the trace additive present in the thermosetting resin composition.

  The thermosetting resin composition of the present invention exhibits excellent characteristics as described above without containing a large amount of layered silicate. Therefore, the interlayer insulating substrate can be made thinner than the interlayer insulating substrate of the conventional multilayer printed board, and the density and thickness of the multilayer printed board can be increased. Moreover, the dimensional stability of the resin sheet which consists of a thermosetting resin composition of this invention can be improved with the nucleation effect of the layered silicate in crystal formation, the swelling suppression effect accompanying the improvement in moisture resistance, etc. For this reason, the stress caused by the dimensional difference before and after the thermal history when the thermal history is applied can be reduced, and when used as an interlayer insulating substrate of a multilayer printed board, the reliability of electrical connection is effectively enhanced. It becomes possible.

  In addition, since a sintered body made of layered silicate is formed during combustion, the shape of the combustion residue is retained, shape collapse does not easily occur after combustion, and it is possible to prevent the spread of fire, thus exhibiting excellent flame retardancy To do.

  Applications of the thermosetting resin composition of the present invention include, for example, resin sheets, prepregs, varnishes, and optical waveguides obtained by dissolving in an appropriate solvent or forming into a film (film formation) and processing. Although materials etc. are mentioned, the thermosetting resin composition of this invention is not limited to these uses.

  Next, the resin sheet of this invention consists of the thermosetting resin composition of this invention mentioned above. Moreover, the resin sheet obtained by hardening the resin sheet which consists of a thermosetting resin composition of this invention is another aspect of the resin sheet of this invention.

Although it does not specifically limit as a shaping | molding (film forming) method of the resin sheet of this invention, For example, each contained in the thermosetting resin composition of this invention or the thermosetting resin composition of this invention Extruding after each predetermined amount of components is melt-kneaded in an extruder and then extruding and forming into a film using a T die, a circular die or the like, the thermosetting resin composition of the present invention or the thermosetting resin of the present invention Examples include casting molding methods in which each predetermined amount of each component contained in the composition is dissolved or dispersed in a solvent such as an organic solvent and mixed, and then cast into a film, and other conventionally known film molding methods. In particular, since the multilayer printed circuit board produced using the resin sheet of the present invention can be thinned, an extrusion molding method or a casting molding method is preferably used. .

  Applications of the resin sheet of the present invention include, for example, a semiconductor package substrate, a printed board, a substrate material for forming a core layer or a prepreg or build-up layer of a multilayer printed board, a sheet, a laminated board, a copper foil with resin, a copper Although the sheet | seat used for a tension laminated board, a rigid flexible substrate, the film for TAB, etc. are mentioned, the resin sheet of this invention is not limited to these uses. As described above, the thermosetting resin composition according to the present invention, and the resin sheet constituted by using the thermosetting resin composition are excellent in transparency, and therefore, electrical and electronic materials, particularly builds When used for an up insulating film, alignment (positioning) is facilitated during lamination. Furthermore, it becomes easy to confirm the presence or absence of voids by air entrainment.

  In addition, the thermosetting resin composition according to the present invention, and the resin sheet or the like constituted by using the thermosetting resin composition are provided with photosensitivity and are used for solder resist, full additive, and the like. It can be suitably used for reactive plating resists.

  Next, the resin sheet for an insulating substrate of the present invention comprises the resin sheet of the present invention. That is, the insulating substrate resin sheet of the present invention is produced by curing the resin sheet of the present invention.

  Since the thermosetting resin composition of the present invention contains the epoxy resin, the epoxy resin curing agent, the engineering plastics and the layered silicate, it has excellent mechanical properties and high frequency of the IC package. In addition, it has excellent electrical characteristics that can be applied, and even when subjected to a thermal history exposed to high temperatures, the dimensional change before and after the thermal history is small, that is, the linear expansion coefficient is small. A molded body such as can be obtained.

  Moreover, since the resin sheet and the resin sheet for an insulating substrate of the present invention are composed of the thermosetting resin composition of the present invention, excellent mechanical properties and excellent electrical characteristics that can cope with high frequency of the IC package, Even when the thermal history exposed to high temperatures is received, the dimensional change before and after the thermal history is small, that is, the thermal expansion coefficient is small, and the thickness can be reduced.

  In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to these examples.

  In this example, the following raw materials were used.

1. Epoxy resin (1) Bisphenol A type epoxy resin 1 (trade name “DE R331L”, manufactured by Dow Chemical Japan Co., Ltd.)
(2) Solid epoxy resin (trade name “YP-55”, manufactured by Tohto Kasei Co., Ltd.)
(3) Bisphenol A type epoxy resin 2 (trade name “YD-8125”, manufactured by Tohto Kasei Co., Ltd.)
(4) Biphenyl type epoxy resin (trade name “NC-3000H”, manufactured by Nippon Kayaku Co., Ltd.)
2. Epoxy resin curing agent (1) Dicyandiamide (trade name “ADEKA HARDNER EH-3636”, manufactured by Asahi Denka Kogyo Co., Ltd.)
(2) Modified imidazole (trade name “ADEKA HARDNER EH-3366”, manufactured by Asahi Denka Kogyo Co., Ltd.)
(3) Hydrophobic phenol compound 1 represented by the general formula (1) (trade name “PP-1000-240”, OH equivalent: 420, softening point: about 150 ° C., manufactured by Nippon Petrochemical Co., Ltd.)
(4) Triphenylphosphine (Wako Pure Chemical Industries, Ltd.)
(5) The epoxy resin curing agent represented by the formula (3), wherein in the formula (3), R ³ is the formula (4a), R ⁴ is the formula (5c), and R ⁵ is the formula ( ⁵ ). Hydrophobic phenol compound 2 which is a group represented by 6a) and R ⁶ is hydrogen (trade name “MEH7851H”, manufactured by Meiwa Kasei Co., Ltd.)
(6) The epoxy resin curing agent represented by the formula (3), wherein in the formula (3), R ³ is the formula (4a), R ⁴ is the formula (5a), and R ⁵ is the formula ( Hydrophobic phenol compound 3 which is a group represented by 6a) and R ⁶ is hydrogen (trade name “MEH7800H”, manufactured by Meiwa Kasei Co., Ltd.)
3. Engineering Plastics (1) Polyethersulfone resin (trade name “P-1700”, manufactured by Solvent Advanced Polymers)
(2) Polysulfone resin (trade name “A-300”, manufactured by Solvent Advanced Polymers)
4). Layered silicate ・ Synthetic hectorite that has been chemically treated (organized) 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.)}

(Example 1)
Bisphenol A type epoxy resin 1 “DE R331L” 35 parts by weight, solid epoxy resin “YP-55” 35 parts by weight, dicyandiamide “Adeka Hardener EH-3636” 2.5 parts by weight, modified imidazole “Adeka Hardener EH-” 3366 "1.1 parts by weight, polyethersulfone resin" P-1700 "25 parts by weight, synthetic hectorite" Lucentite STN "30 parts by weight and DMF 456 parts by weight are mixed and stirred uniformly for 1 hour. After making it into a solution, it was degassed to prepare a thermosetting resin composition solution.

  Next, using an applicator, the thermosetting resin composition solution obtained above is coated on a polyethylene terephthalate (PET) film that has been subjected to a release treatment so that the thickness after drying is 100 μm and 2 mm. And it dried in 100 degreeC gear oven for 12 minutes, and produced the non-hardened | cured material of the resin sheet. Next, the uncured product of the resin sheet was heated at 110 ° C. for 3 hours, and further cured by heating at 170 ° C. for 30 minutes to prepare a cured resin sheet having a thickness of 100 μm and 2 mm.

(Examples 2 to 4) and (Comparative Example 1 and Comparative Example 2)
A thermosetting resin composition solution is prepared in the same manner as in Example 1 except that the thermosetting resin composition solution has the blending composition shown in Table 1, and the uncured and cured products of the resin sheet are prepared. Produced.

(Example 5)
The synthetic hectorite “Lucentite STN” (14.4 parts by weight) and DMF (197.2 parts by weight) were mixed and stirred at room temperature until a completely homogeneous solution was obtained. Thereafter, 10.0 parts by weight of bisphenol A type epoxy resin 2 “YD-8125” and 10 parts by weight of polyethersulfone resin “P-1700” are added and stirred at room temperature until a completely homogeneous solution is obtained. did. Next, 23.5 parts by weight of the hydrophobic phenol compound 1 “PP-1000-240”, which is an epoxy resin curing agent, is added to the above solution and stirred at room temperature until a completely uniform solution is obtained. A composition solution was prepared.

  Next, the obtained thermosetting resin composition solution is applied to a transparent polyethylene terephthalate (PET) film (trade name “PET5011 550”, thickness 50 μm, manufactured by Lintec Corporation) that has been subjected to a release treatment. It coated so that the thickness after drying might be set to 50 micrometers. Thereafter, it was dried in a gear oven at 100 ° C. for 12 minutes to produce an uncured resin sheet having a size 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 cured product of a resin sheet having a thickness of 100 μm and 2 mm.

(Example 6)
50.0 parts by weight of a biphenyl type epoxy resin “NC-3000H”, 40.0 parts by weight of a hydrophobic phenol compound 2 “MEH7851H” which is an epoxy resin curing agent, and a polyethersulfone resin “P-1700” 10.0 Part by weight, 2.0 parts by weight of synthetic hectorite “Lucentite STN”, 0.3 parts by weight of triphenylphosphine, and 150.0 parts by weight of DMF were added to a beaker. Next, after stirring for 1 hour with a stirrer, defoaming was performed to obtain a resin / layered silicate solution. Next, after removing the solvent in a state where the obtained resin / layered silicate solution was applied on a sheet of polyethylene terephthalate, it was heated at 100 ° C. for 15 minutes to prepare an uncured body of a test sheet made of the resin composition. did. This test sheet was laminated and laminated to a thickness of 1 mm to prepare an uncured plate-like molded body for measuring melt viscosity. Furthermore, the uncured test sheet and the laminate were cured by heating at 180 ° C. for 3 hours to produce a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition.

(Example 7)
51.0 parts by weight of a biphenyl type epoxy resin “NC-3000H”, 32.00 parts by weight of a hydrophobic phenol compound 3 “MEH7800H” which is an epoxy resin curing agent, 10.0 parts by weight of a polysulfone resin “A-300” Then, 4.0 parts by weight of synthetic hectorite “Lucentite STN”, 0.3 parts by weight of triphenylphosphine, and 186.0 parts by weight of DMF were added to a beaker. Next, after stirring for 1 hour with a stirrer, defoaming was performed to obtain a resin / layered silicate solution. Next, after removing the solvent in a state where the obtained resin / layered silicate solution was applied on a sheet of polyethylene terephthalate, it was heated at 100 ° C. for 15 minutes to prepare an uncured body of a test sheet made of the resin composition. did. This test sheet was laminated and laminated to a thickness of 1 mm to prepare an uncured plate-like molded body for measuring melt viscosity. Furthermore, the uncured test sheet and the laminate were cured by heating at 180 ° C. for 3 hours to produce a plate-like molded body having a thickness of 2 mm and 100 μm made of the resin composition.

(Evaluation results of Examples 1 to 7 and Comparative Examples 1 to 2)
Performance of Resin Sheets Obtained in Examples 1 to 7 and Comparative Example 1 and Comparative Example 2 {1. 1. Average linear expansion coefficient (α1), 2. Average linear expansion coefficient (α2); 3. dissipation factor, 4. Breaking strength Elongation at break, 6. 6. Average interlayer distance of layered silicate, 7. Ratio of layered silicate of 5 layers or less, 8. a ratio of three or more layered silicates, 10. Dispersion state of engineering plastics, presence or absence of engineering plastics of 10.3 μm or more, The presence or absence of layered silicate in engineering plastics} was evaluated by the following method.

  The evaluation results of Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1 below. Furthermore, the evaluation results of Examples 5 to 7 are shown in Table 2 below.

1. 1. Average linear expansion coefficient (α1), and Average coefficient of linear expansion (α2)
The cured resin sheet (thickness: 100 μm) is cut into 3 mm × 25 mm, and using a linear expansion meter (product number “TMA / SS120C”, manufactured by Seiko Instruments Inc.), tensile load is 2.94 × 10 ⁻² N, rising The average linear expansion coefficient (α1) at a temperature 10 to 50 ° C. lower than the glass transition temperature of the cured product and the average line at a temperature 10 to 50 ° C. higher than the glass transition temperature of the cured product at a temperature rate of 5 ° C./min. The expansion coefficient (α2) was measured.

3. Dielectric loss tangent Resin sheet cured product (thickness: 100 μm) is cut into 15 mm × 15 mm, and 4 sheets are laminated to form a 400 μm thick laminate, using a dielectric constant measuring device (product number “HP4291B”, manufactured by HEWLETT PACKARD). The dielectric loss tangent at a frequency of 1 GHz at room temperature was measured.

4). 4. breaking strength, and Breaking elongation The cured resin sheet (thickness: 100 μm) is cut into 10 mm × 80 mm, and using a tensile tester (trade name “Tensilon”, manufactured by Orientec Co., Ltd.), the distance between chucks is 60 mm and the crosshead speed is 5 mm / min. Tensile tests were performed under the conditions described above, and the breaking strength (MPa) and elongation at break (%) were measured.

6). Average interlayer distance of layered silicate Diffraction obtained from diffraction of layered surface of layered silicate using X-ray diffractometer (product number “RINT1100”, manufactured by Rigaku Corporation) on cured resin sheet (thickness 2 mm) The 2θ of the peak was measured, the (001) plane distance d of the layered silicate was calculated by the Bragg diffraction formula below, and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ
Here, λ is 0.154 (nm), and θ represents a diffraction angle.

7). A ratio of 5 or less layers of layered silicate, and 8. Ratio of three or more layers of layered silicate Total number of layered layers of layered silicate that can be observed in a fixed area by observing a cured resin sheet (thickness 100 μm) with a transmission electron microscope at a magnification of 100,000 times (X) and the number of layered silicate layers (Y) dispersed as a laminate of 5 layers or more, and the number of layered silicate layers (Z) dispersed as a laminate of 3 layers or more did. The ratio (%) of the layered silicate dispersed as a laminate of five layers and three or more layers was calculated according to the following calculation formula, and the dispersion state of the layered silicate was evaluated according to the following criteria.

Ratio of layered silicate dispersed as a laminate of 5 layers or more (%) = (Y / X) × 100
[Criteria]
○ The ratio of layered silicate dispersed as a laminate of 5 layers or less was 10% or more.

  X: The proportion of the layered silicate dispersed as a laminate of 5 layers or less was less than 10%.

Ratio of layered silicate dispersed as a laminate of three or more layers (%) = (Z / X) × 100
[Criteria]
○ The ratio of the layered silicate dispersed as a laminate of three or more layers was 30% or more and 70% or less.

  X: The proportion of layered silicate dispersed as a laminate of three or more layers was less than 30% or more than 70%.

9. Engineering plastics dispersion state and presence of engineering plastics of 10.3μm or less [Criteria]
○ ··· Dispersed at 3 µm or less, and present as a dispersed phase.

  × ··· Dispersed exceeding 3 μm, or present as a continuous layer or a compatible layer.

  A cured product (thickness: 100 μm) of the resin sheet was observed with a transmission electron microscope at a magnification of 100,000 times, and the dispersed state of engineering plastics in the cured product and the presence or absence of engineering plastics of 3 μm or more were confirmed.

11. Presence or absence of layered silicate in engineering plastics The cured resin sheet (thickness 100 μm) was observed with a transmission electron microscope at a magnification of 100,000 times to confirm the presence or absence of layered silicate in engineering plastics.

  As described above, the thermosetting resin composition of the present invention has excellent mechanical properties and excellent electrical characteristics that can cope with high frequency of IC packages, and is exposed to heat at high temperatures. Even when a history is received, a dimensional change before and after the thermal history is small, that is, a molded article having a low linear expansion coefficient can be obtained. For example, various types such as resin sheets, prepregs, varnishes, optical waveguide materials, etc. It is suitably used for applications.

  In addition, since the resin sheet of the present invention is composed of the thermosetting resin composition of the present invention, it has excellent mechanical properties and excellent electrical characteristics that can cope with high frequency of the IC package, and Even when subjected to a thermal history exposed to high temperatures, the dimensional change before and after the thermal history is small, that is, the coefficient of linear expansion is small. For example, the core of a semiconductor package substrate, printed circuit board, multilayer printed circuit board Suitable for various uses such as a sheet for a substrate, a sheet, a laminate, a resin-coated copper foil, a copper-clad laminate, a rigid flexible substrate, or a TAB film, for forming a layer or a prepreg or build-up layer Used.

  Furthermore, since the resin sheet for an insulating substrate of the present invention is composed of the resin sheet of the present invention, it is suitably used as an interlayer insulating substrate of a multilayer printed board.

Claims (10)

  Engineering plastics containing 0.5 to 100 parts by weight of engineering plastics, 0.1 to 100 parts by weight of layered silicate and epoxy resin curing agent for 100 parts by weight of epoxy resin A thermosetting resin composition characterized by comprising a dispersed phase as a dispersed phase.   The thermosetting resin composition according to claim 1, wherein 1 to 40 parts by weight of the engineering plastics is contained with respect to 100 parts by weight of the epoxy resin.   The engineering plastics is at least one kind of engineering plastics selected from the group consisting of a polysulfone resin, a polyethersulfone resin, a polyimide resin, and a polyetherimide resin. Thermosetting resin composition.   The thermosetting resin composition according to any one of claims 1 to 3, wherein no layered silicate is present in the engineering plastics present as the dispersed phase.   The layered silicate is at least one kind of layered silicate selected from the group consisting of montmorillonite, hectorite, swellable mica and vermiculite. Thermosetting resin composition.   The layered silicate contains at least one ammonium salt selected from the group consisting of alkyl ammonium salts having 6 or more carbon atoms, aromatic quaternary ammonium salts, and heterocyclic quaternary ammonium salts. The thermosetting resin composition according to any one of claims 1 to 5.   Part or all of the layered silicate is dispersed in a state where the average interlayer distance of the (001) plane measured by wide-angle X-ray diffraction method is 3 nm or more and the number of laminated layers is 5 or less. The thermosetting resin composition according to any one of claims 1 to 6.   A resin sheet comprising the thermosetting resin composition according to any one of claims 1 to 7.   A resin sheet obtained by curing a resin sheet comprising the thermosetting resin composition according to any one of claims 1 to 7. An insulating substrate resin sheet comprising the resin sheet according to claim 8.