JP2005146240A - Method for producing composite material, composite material, composite material dispersion, and cured product of composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a composite material from which a cured product excellent in heat resistance and prevented from formation of voids, cracks, curls, etc., is obtainable, to provide the composite material, to provide a composite material dispersion, and to provide the cured product of the composite material. <P>SOLUTION: This method for producing the composite material comprises heating an alkoxy group-containing silane-modified epoxy resin (A) and metal oxide particles (B) under a substantially anhydrous condition, so as to conduct dealcoholization condensation reaction of the alkoxy groups in the resin (A) with the hydroxy groups existing on surfaces of the particles (B), wherein the epoxy resin (A) is obtained by conducting dealcoholization condensation reaction of a bisphenol-type epoxy resin (a1) with a partial condensate (a2) of a hydrolyzable alkoxysilane. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a composite, a composite, a composite dispersion, and a composite cured product. The composite, its dispersion, and the cured product obtained from these are the composition for rigid printed circuit boards, adhesive, conductive material, anisotropic conductive paste, non-conductive paste, solder resist ink, flooring, battery It can be suitably used for various applications such as separator materials, optical path substrate materials, plastic film modifiers, heat resistant coating agents, and molding processing compositions.

  Epoxy resins are generally used as a composition in combination with a curing agent, and the composition has been used in the field of electrical / electronic materials. However, with the recent development of the electric / electronic materials field, higher performance is required for the cured product of the epoxy resin composition, and in particular, improvement in heat resistance is desired.

  In order to improve the heat resistance of the cured product of the epoxy resin composition, for example, a method using a composition in which a filler such as glass fiber, glass particles, mica, etc., in addition to an epoxy resin and a curing agent is used. However, even with this method, sufficient heat resistance cannot be obtained. Further, the transparency of the cured product obtained by this method is lost, and the adhesiveness at the interface between the filler and the epoxy resin is inferior, so that the mechanical properties such as the elongation rate are insufficient.

  As a method for improving the heat resistance of a cured product of an epoxy resin composition, a method using a composite of an epoxy resin and silica has been proposed (see Patent Document 1). In the composite, hydrolyzable alkoxysilane is added to the partially cured epoxy resin solution, the cured product is further cured, the alkoxysilane is hydrolyzed to form a sol, and further polycondensed to gel. Can be obtained. However, the cured product obtained from such a composite has a certain degree of improvement in heat resistance compared to the cured product of the epoxy resin alone, but the cured product is caused by water in the composite, water generated during curing, or alcohol. Voids (bubbles) are generated inside. In addition, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, the transparency of the cured product obtained by agglomeration of the silica produced by the sol-gel curing reaction is lost and whitened, and a large amount of alkoxysilane is added. A large amount of water is required to form a sol, resulting in warping of the cured product, cracks, and the like.

  Further, a method using an alkoxy group-containing silane-modified epoxy resin obtained from an epoxy resin and an alkoxysilane oligomer has been proposed (see Patent Document 2). By curing the alkoxy group-containing silane-modified epoxy resin, a cured product that is transparent, warped, and free of cracks can be obtained. In the curing reaction, two types of sol-gel curing reaction and epoxy curing reaction proceed competitively. To do. In the former reaction, as in the cured product using the composite of epoxy resin and silica described above, alcohol is generated at the time of sol formation. When the curing speed is increased, generation of fine voids and curls in the cured product cannot be completely prevented, so that it has been difficult to use in thick film applications.

  JP-A-8-100107   JP 2002-249539 A

  The present invention provides a method for producing a composite having excellent heat resistance and capable of obtaining a cured product that does not cause voids, cracks, curls, etc., the composite, the body composite dispersion, and a cured product of the composite. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventor uses a composite obtained by condensing a specific alkoxy group-containing silane-modified epoxy resin and a metal oxide, or the composite dispersion. As a result, it was found that a cured product meeting the purpose was obtained, and the present invention was completed.

  That is, the present invention relates to an alkoxy group-containing silane-modified epoxy resin (A) obtained by subjecting a bisphenol-type epoxy resin (a1) and a hydrolyzable alkoxysilane partial condensate (a2) to a dealcoholization condensation reaction and metal oxide particles ( B) is heated under substantially anhydrous conditions to cause a dealcoholization condensation reaction between the alkoxy group in (A) and the hydroxyl group present on the surface of (B). The present invention relates to a method for manufacturing a body. The present invention also relates to a composite obtained by the production method. The present invention also includes the composite particle, at least one dispersion medium selected from the group consisting of a liquid epoxy resin, a reactive diluent and an organic solvent, and a curing agent for epoxy resin or an epoxy group ring-opening polymerization catalyst. It is related with the composite dispersion characterized by doing. Furthermore, the present invention relates to a composite cured product characterized by curing the composite dispersion.

  According to the present invention, it is possible to produce a composite as a precursor and the dispersion, which are excellent in heat resistance and can give a cured product that does not cause foaming, warping, cracking, etc. even when cured thick. . The composite of the present invention obtained by the production method and the dispersion thereof are substantially free of alkoxy groups that cause a sol-gel reaction, so that even when coated with a thick film on a substrate, The disadvantages such as foaming, which have been a concern, can be sufficiently eliminated, and a cured product that is uniform and transparent, free from warping and cracking and excellent in heat resistance can be easily provided. The cured product can be applied to various uses, and is particularly useful in the field of electronic materials. For example, compositions for rigid printed circuit boards, adhesives, conductive materials, anisotropic conductive pastes, non-conductive pastes, solder resist inks , Flooring materials, battery separator materials, optical path substrate materials, plastic film modifiers, heat-resistant coating agents, and molding processing compositions.

  The composite of the present invention comprises an alkoxy group-containing silane-modified epoxy resin (A) (hereinafter referred to as component (A)) and metal oxide particles (B) (hereinafter referred to as component (B)) under substantially anhydrous conditions. It is produced by heating under and causing a dealcoholization condensation reaction between the alkoxy group in the component (A) and the hydroxyl group present on the surface of the component (B). The component (A) includes a bisphenol type epoxy resin (a1) (hereinafter referred to as component (a1)), a hydrolyzable alkoxysilane partial condensate (a2) (hereinafter referred to as component (a2)), and, if necessary, an epoxy alcohol. (Hereinafter referred to as component (a3)).

  Component (a1), which is a raw material of component (A), is obtained by reaction of bisphenols with haloepoxides such as epichlorohydrin or β-methylepichlorohydrin. Bisphenols obtained by reaction of phenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone, oxidation of dihydroxyphenyl sulfide with peracid, etherification of hydroquinone, etc. Can be given. Component (a1) is characterized by flame retardancy, such as halogenated bisphenol-type epoxy resins derived from halogenated phenols such as 2,6-dihalophenol, and phosphorus-modified bisphenol-type epoxy resins chemically reacted with phosphorus compounds. You can also use what you have. Furthermore, a hydrogenated epoxy resin obtained by hydrogenating the above epoxy resin having a bisphenol skeleton under pressure can also be used.

  The component (a1) has a hydroxyl group capable of forming a silicate ester by a dealcoholization condensation reaction with the component (a2). The said hydroxyl group does not need to be contained in all the molecules which comprise a component (a1), and should just have a hydroxyl group as a whole of a component (a1). Among the components (a1), bisphenol A type epoxy resins are particularly preferable from the viewpoint of versatility and cost.

  The bisphenol A type epoxy resin has the general formula (1):

It is a compound represented by these.

  In the present invention, the epoxy equivalent of the component (a1) is not particularly limited, and can be appropriately selected and determined according to the application. However, when manufacturing the said hardened | cured material using the composite_body | complex of this invention, the epoxy equivalent as a whole is about 200-400 g / eq using one or more types of bisphenol-type epoxy resins as a component (a1). It is preferable to adjust so that. As will be described later, when the component (A) is produced in the absence of a solvent, the viscosity in the reaction system tends to be higher than when the reaction is carried out in a solvent system. It is preferable to select the kind of a1) and the epoxy equivalent. Moreover, when the equivalent as a mixture of a component (a1) exceeds 400 g / eq, not only the viscosity in a system at the time of manufacture of a component (A) (solvent-free reaction system) will become high easily, but the composite_body | complex of this invention. In the production process, there is a tendency to increase the viscosity or gelation, and when the epoxy equivalent is less than 200 g / eq, the residual amount of the component (a2) in the component (A) to be obtained increases or the resulting curing Things tend to be brittle.

  In the present invention, epoxy alcohol (hereinafter referred to as component (a3)) can also be used as a constituent material of component (A) in addition to the components (a1) and (a2). Similarly to component (a1), component (a3) undergoes a dealcoholization condensation reaction with component (a2) to give component (A).

  By the way, in the component (a1), a hydroxyl group for the dealcoholization condensation reaction with the component (a2) must be present. For example, in the case of the bisphenol A type epoxy resin of the general formula (a), There are also molecules having no hydroxyl group (molecules of m = 0 in the general formula (1)). Since the epoxy resin molecule having no hydroxyl group does not react with the component (a2), it remains unreacted in the resulting component (A). Therefore, the heat resistance of the finally obtained composite cured product tends to decrease.

  In the present invention, even when a large amount of epoxy resin molecules having no hydroxyl group are present in component (A), by using component (a3) as a constituent raw material, the heat resistance of the finally obtained composite cured product There is an advantage that high sex can be maintained.

  A specific example of the component (a3) is represented by the following general formula (2).

  General formula (2):

  The component (a3) preferably has p in the general formula (2) of 1 to 10. When the value of p exceeds 10, the heat resistance of the finally obtained composite cured product tends to decrease.

  As described above, the component (a3) imparts sufficient heat resistance to the resulting composite cured product even when the component (a1) in which many epoxy resin molecules having no hydroxyl group are present is used. Can be used for Therefore, when it becomes a composite hardened | cured material which has sufficient heat resistance, it is not necessary to necessarily use a component (a3). In the production of component (A), the amount of component (a3) used is not particularly limited, and may be appropriately determined according to the content of epoxy resin molecules having no hydroxyl group present in component (a1). In addition, since a certain amount of toxicity may be recognized for a component (a3), it is good to reduce the unreacted component (a3) which remains in the component (A) obtained as much as possible.

  In addition, as component (a2) which is a constituent raw material of component (A), the following hydrolyzable alkoxysilane compound and water are added and partially hydrolyzed and condensed in the presence of an acid or base catalyst. Can be used.

As the alkoxysilane compound, for example, the general formula (3):
R ¹ _n Si (OR ² ) _4-n
(In the formula, n represents 0 or 1. R ¹ represents a lower (1 to 4 carbon atoms) alkyl group, aryl group or unsaturated aliphatic residue which may have a functional group directly connected to a carbon atom. R ² represents a methyl group or an ethyl group, and R ² may be the same as or different from each other.

  Examples of the hydrolyzable alkoxysilane compound that is a constituent material of the component (a2) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n- Examples thereof include propyltrimethoxysilane, n-propyltriethoxysilane, impropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

  The hydrolyzable alkoxysilane compound that is a constituent raw material of the component (a2) is rich in reactivity with the component (a1) and the component (a3) and can be prepared and obtained at a relatively low temperature. Tetramethyoxysilane and methyltrimethoxysilane are particularly preferred from the standpoint of easy processing.

  Component (A2) is represented, for example, by the following general formula (4) or (5). General formula (4):

(In the formula, R ¹ represents a lower (1 to 4 carbon atoms) alkyl group, aryl group or unsaturated aliphatic residue which may have a functional group directly connected to a carbon atom. R ² represents a methyl group. Or an ethyl group, and R ² may be the same or different.

  General formula (5):

(In the general formula (5), ^{R 2} is Formula (4) the same as ^{R 2} in.)

  The number average molecular weight of the component (a2) is about 230 to 2000, and in the general formulas (4) and (5), those having an average repeating unit number q of 2 to 11 are preferable. When the value of n exceeds 11, the compatibility with the components (a1) and (a3) decreases, and the reactivity with the components tends to decrease. When n is less than 2, it is likely to be distilled out of the system together with the alcohol by-produced in the reaction.

  The component (A) in the present invention can be obtained by charging the component (a1), the component (a2) and, if necessary, the component (a3) into a reaction apparatus, and subjecting it to a dealcoholization condensation reaction under the conditions described later. The weight ratio between the total amount of component (a1) and component (a3) used and the amount of component (a2) used is not particularly limited as long as the alkoxy group substantially remains in component (A). However, [total equivalent of hydroxyl group of component (a1) and hydroxyl group of component (a3) / equivalent of alkoxy group of hydrolyzable alkoxysilane compound (3)] (equivalent ratio) = 0.1 to 0 .6, more preferably 0.13 to 0.5. If the equivalent ratio is less than 0.1, the content of the unreacted alkoxysilane partial condensate (3) increases, and if it exceeds 0.6, the heat resistance of the resulting composite cured product tends to decrease.

  The component (A) can be produced by subjecting the raw material component to dealcohol condensation in the absence of a dispersion medium. However, when the reaction system becomes highly viscous, it is reacted in a reactive diluent or an organic solvent. May be. In the dealcoholization condensation reaction in the present invention, the reaction temperature is about 50 to 130 ° C, preferably 70 to 110 ° C, and the total reaction time is about 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the polycondensation reaction of component (a2) itself. Moreover, in order to shorten reaction time, manufacture of a component (A) can also be performed under reduced pressure of the range which a component (a3) does not evaporate.

  In the dealcoholization condensation reaction, a catalyst that does not open the epoxy ring of component (a1) or component (a3) among conventionally known catalysts can be used to promote the reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese. And metals such as oxides, organic acid salts, halides and alkoxides of these metals. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective.

  The above dealcoholization condensation reaction can be carried out in the absence of a dispersion medium, but when the molecular weight of component (a1) or component (a2) is large, the reaction system may be heterogeneous at the reaction temperature. Therefore, it is preferable to use at least one dispersion medium selected from a liquid epoxy resin, a reactive diluent, and an organic solvent.

  The component (A) thus obtained is mainly composed of the component (a2) in which the alkoxy group is substituted with an epoxy group by reacting with the hydroxyl group of the component (a1) or component (a3). However, the component (A) may contain a small amount of these raw material components.

  In the composite of the present invention, the component (A) and the component (B) are heated under substantially anhydrous conditions, and the alkoxy group in the (A) and the hydroxyl group present on the surface of the (B) It can manufacture by carrying out a dealcohol condensation reaction between. As the component (B), for example, silicon oxide, titanium oxide, tin oxide, zirconia oxide, aluminum oxide, zinc oxide, copper oxide, cobalt oxide, bismuth oxide, indium-tin oxide, yttrium oxide and the like can be used. Among these, silicon oxide, titanium oxide, tin oxide, aluminum oxide, zirconia oxide, and zinc oxide are particularly preferable because of high reactivity with the component (A).

  The particle diameter of the component (B) can be appropriately determined according to the use of the finally obtained composite cured product, but considering the transparency, smoothness, and elastic modulus of the composite cured product, It is better that it is as small as possible. Specifically, a nanofiller having an average particle diameter of about 5 to 100 nm can be preferably used.

  As the component (B), the above metal oxide can be used as it is, but considering the handling workability, the metal oxide is at least one selected from a liquid epoxy resin, a reactive diluent, and an organic solvent. It is preferable to use the dispersion liquid dispersed in the above dispersion medium. As a method for producing the dispersion, in addition to a method of mixing and stirring and dispersing in a dispersion medium so that the concentration of the metal oxide is about 5 to 50% by weight, aqueous colloidal particles of the metal oxide are used. And a method of substituting the water with the dispersion medium and a method of obtaining a fine particle dispersion by sol-gel curing of a metal alkoxide diluted with a dispersion medium.

  As described, the production method of the present invention is characterized in that a dealcoholization condensation reaction is carried out between an alkoxy group in component (A) and a hydroxyl group present on the surface of component (B) under substantially anhydrous conditions. There is. By reacting under substantially anhydrous conditions, self-condensation (sol-gel reaction) between alkoxy groups in component (A) is suppressed, and the alkoxy groups in component (A) and component (B) are suppressed. The dealcohol condensation reaction can be allowed to proceed selectively with the hydroxyl groups present on the surface, and the remaining alkoxy groups in component (B) can be substantially eliminated. That is, according to the production method of the present invention, M (metal) -O-Si can be selectively formed on the surface of the resulting composite. Due to the fact that the remaining alkoxy groups in the component (B) can be substantially eliminated, there is no alkoxy group that can participate in the sol-gel reaction even when the resulting composite is cured. Disadvantages such as foaming can be eliminated.

  In the reaction, the number of moles of hydroxyl groups present on the surface of component (B) / number of moles of alkoxy groups present in component (A) is preferably about 0.5 to 3.0. When it is less than 0.5, the alkoxy group of component (A) becomes excessive, and the self-condensation between the alkoxy groups tends to proceed during the reaction, and when it is more than 3.0, the hydroxyl group on the surface of component (B) Becomes excessive and tends to cause aggregation and precipitation during the reaction.

  In the above reaction for producing the complex of the present invention, as described above, the production of alcohol and component (A) as a by-product under substantially anhydrous conditions and in the presence or absence of a dispersion medium. This is performed while removing volatile components such as the solvent used. The reaction temperature is about 70 to 250 ° C., and the total reaction time is about 1 to 20 hours. In order to shorten the reaction time, the same catalyst as used in the production of the component (A) may be used, or the reaction may be performed under reduced pressure. In the complex obtained by the reaction, 70 to 100% of the alkoxy groups derived from the component (A) disappear, and the M (metal) -O-Si bond described above is formed at the ratio. is there. If the amount of the remaining alkoxy groups in the composite is too less than 70%, foaming, cracking, warping, and the like due to by-product alcohol tend to occur in the curing process.

  In addition, the dispersion medium that can be used in the above reaction can be appropriately determined in consideration of the dispersibility (non-aggregation property, non-reactivity, etc.) for the component (B) to be dispersed and the solubility for the component (A). For example, liquid epoxy resins such as low molecular weight bisphenol type epoxy resins and novolak phenol type epoxy resins; reactive diluents such as glycidyl ethers and glycidyl esters; alcohols such as methanol, ethanol and isopropyl alcohol; toluene, xylene and methyl ethyl ketone And organic solvents such as methyl isobutyl ketone.

  When the dispersion medium is a liquid epoxy resin or a reactive diluent, the amount of the dispersion medium constituting the composite dispersion of the present invention is 100 weights in total of component (A) and component (B). Per part, it is usually about 5 to 200 parts by weight, preferably 10 to 100 parts by weight, and if it is less than 5 parts by weight, the composite dispersion tends to have a high viscosity and it is difficult to obtain sufficient fluidity. When it exceeds 200 weight part, there exists a tendency for the heat resistance of the hardened | cured material of the obtained composite to fall. Moreover, when the said dispersion medium is an organic solvent, the usage-amount is not specifically limited, What is necessary is just to determine suitably according to various uses.

  The composite of the present invention and the dispersion thereof can be blended with a curing agent for epoxy resin or an epoxy group ring-opening polymerization catalyst as the constituent component depending on the curing conditions and applications. As a curing agent for epoxy resin, a phenol resin curing agent, a polyamine curing agent, a polycarboxylic acid curing agent, an imidazole curing agent, etc., which are usually used as a curing agent for epoxy resins, can be used without any particular limitation. . Specifically, phenolic resin-based ones include phenol novolak resin, bisphenol novolac resin, poly p-vinylphenol, and the like, and polyamine-based curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, Polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4, Examples include 4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, dicyandiamide, and the polycarboxylic acid-based curing agents include phthalic anhydride and tetrahydrophthalic anhydride. Examples include methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, methyl-3,6-endomethylenetetrahydrophthalic anhydride, and imidazole curing agents include Examples include 2-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanurate, and the like.

  The use ratio of the curing agent for epoxy resin is usually in the curing agent for epoxy resin with respect to 1 equivalent of the epoxy group that the composite has and the epoxy group that the composite dispersion (containing a reactive diluent, etc.) has. The active hydrogen-containing functional group is blended at such a ratio that it is about 0.2 to 1.5 equivalents.

  Moreover, you may further mix | blend the hardening accelerator for accelerating hardening reaction with the composite_body | complex of this invention and its dispersion. Examples of the curing accelerator include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. Tertiary amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate Such as tetraphenyl boron salts such as chromatography bets and the like. The usage-amount of the said hardening accelerator is about 0.1-5 weight part normally with respect to 100 weight part of the said composite_body | complex or its dispersion.

The epoxy group ring-opening polymerization catalyst that can be used as a constituent of the composite of the present invention and its dispersion is not particularly limited, and various known catalysts can be used. For example, aromatic sulfonium, aromatic iodonium, aromatic At least one cation selected from a group diazonium, aromatic ammonium, η ⁵ -cyclopentadiel-η ⁶ -cumenyl-Fe salt system, and the like, and at least one selected from BF ₄ ⁻ , PF ₆ ⁻ , and SbF ₆ ^— The amount of the onium salt used is usually about 0.1 to 10 parts by weight with respect to 100 parts by weight of the complex or its dispersion.
Such thermal cationic polymerization initiators may be used alone or in combination of two or more.

  Examples of the aromatic sulfonium salt-based epoxy group ring-opening polymerization catalyst include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate and bis [4- (diphenylsulfonio) phenyl] sulfide bishexa. Fluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, (2-ethoxy-1-methyl- 2-oxoethyl) methyl-2-naphthalenylsulfonium hexafluorophosphate, (2-ethoxy-1-methyl-2-oxoethyl) methyl-2-naphthalenylsulfonium hexafluoroatimonate, (2-ethoxy Ci-1-methyl-2-oxoethyl) methyl-2-naphthalenylsulfonium tetrafluoroborate, (2-ethoxy-1-methyl-2-oxoethyl) methyl-2-naphthalenylsulfonium tetrakis (pentafluorophenyl) borate , Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroatimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenyl Sulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate , Triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4 -(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bis Examples thereof include tetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, and the like.

  Examples of the aromatic iodonium salt-based epoxy group ring-opening polymerization catalyst include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis ( Dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-Methylethyl) phenyliodonium hexafluorophosphate, 4 Methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) Examples thereof include phenyliodonium tetrakis (pentafluorophenyl) borate.

  Examples of the aromatic diazonium salt-based epoxy group ring-opening polymerization catalyst include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate. It is done.

  Examples of the aromatic ammonium salt-based epoxy group ring-opening polymerization catalyst include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2- Cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoro Antimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate I can give it.

Examples of the η ⁵ -cyclopentadiel-η ⁶ -cumenyl-Fe salt-based epoxy group ring-opening polymerization catalyst include η ⁵ -cyclopentadiel-η ⁶ -cumenyl-Fe (II) hexafluorophosphate, η ⁵ - cyclopentadienyl eta ⁶ - cumenyl -Fe (II) hexafluoroantimonate, eta ⁵ - cyclopentadienyl eta ⁶ - cumenyl -Fe (II) tetrafluoroborate, eta ⁵ - cyclopentadienyl eta ⁶ - Examples include cumenyl-Fe (II) tetrakis (pentafluorophenyl) borate.

  In the composite of the present invention and the dispersion thereof, as long as the effects of the present invention are not impaired, a filler, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, You may mix | blend an antibacterial agent, an antifungal agent, a leveling agent, an antifoamer, a coloring agent, a stabilizer, a coupling agent, etc.

  The composite cured product of the present invention can be obtained by curing the above composite or dispersion thereof at room temperature to 250 ° C. The curing temperature can be appropriately determined depending on the type of epoxy resin curing agent. When using a phenol resin curing agent or a polycarboxylic acid curing agent as the curing agent, it is preferable to cure at 100 to 250 ° C. When a polyamine curing agent is used, low temperature curing at room temperature to 100 ° C. is possible.

  In order to obtain a cured product having a film thickness of more than 300 μm using the composite of the present invention or a dispersion thereof, a reactive diluent or a liquid epoxy resin is used as a dispersion medium, or a composite having an alkoxy group residual amount of 80% or more. It is preferable to use the dispersion.

  As described above, the composite and the dispersion of the present invention are used for rigid printed circuit board compositions, adhesives, conductive materials, anisotropic conductive pastes, nonconductive pastes, solder resist inks, flooring materials, and batteries. Although it can be used for various applications such as separator materials, optical path substrate materials, plastic film modifiers, heat resistant coating agents, and molding processing compositions, the usage methods in these applications are not particularly limited, and all are publicly known Various methods can be employed.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. % Is based on weight unless otherwise specified.

Production Example 1 (Production of methoxy group-containing silane-modified epoxy resin [component (A)])
A reactor equipped with a stirrer, a reflux pipe, a water separator, a thermometer, and a nitrogen gas introduction pipe, 100 g of bisphenol type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 834”, epoxy equivalent 257), glycidol 11.9 g and methyltrimethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name “MTMS-A”, Si average number n is 3.2) were charged and 86.6 g were heated to 100 ° C. Thereafter, 0.12 g of dibutyltin dilaurate was added as a catalyst and reacted for 5 hours while removing methanol produced by the reaction. The reaction system was cooled to room temperature to obtain 185 g of a methoxy group-containing silane-modified epoxy resin (A-1). The methoxy group equivalent of the hydrolyzable methoxysilane at the time of charging / the hydroxyl group equivalent of the epoxy resin is 11, the average number of Si per molecule of product / the average number of epoxy rings per molecule of product is 1.5. It is.

Production Example 2 (Production of methoxy group-containing silane-modified epoxy resin [component (A)])
In the same reactor as in Production Example 1, 250 g of a bisphenol type epoxy resin (the above-mentioned trade name “Epicoat 834”, epoxy equivalent 257), 14.1 g of glycidol and a methyltrimethoxysilane partial condensate (the above-mentioned trade name “MTMS-A”). The average number n of Si was 3.2) 102.3 g, and the temperature was raised to 100 ° C. Thereafter, 0.15 g of dibutyltin dilaurate was added as a catalyst and reacted for 6 hours while removing methanol produced by the reaction. The reaction system was cooled to room temperature to obtain 334 g of a methoxy group-containing silane-modified epoxy resin (A-2). In addition, the equivalent of the methoxy group of the hydrolyzable methoxysilane at the time of charging / the equivalent of the hydroxyl group of the epoxy resin is 5.2, the average number of Si per molecule of the product / the average number of epoxy rings per molecule of the product is 1. .16.

Production Example 3 (Production of methoxy group-containing silane-modified epoxy resin [component (A)])
In the same reactor as in Production Example 1, 300 g of a bisphenol type epoxy resin (the above-mentioned trade name “Epicoat 834”, epoxy equivalent 257) and methyltrimethoxysilane partial condensate (the above-mentioned trade name “MTMS-A”, average number of Si) n = 3.2) 259.8 g was charged and heated to 100 ° C. Thereafter, 0.37 g of dibutyltin dilaurate was added as a catalyst, and the reaction was carried out for 13 hours while removing methanol produced by the reaction. The reaction system was cooled to room temperature to obtain 531 g of a methoxy group-containing silane-modified epoxy resin (A-3). In addition, the equivalent of the methoxy group of the hydrolyzable methoxysilane at the time of charging / the equivalent of the hydroxyl group of the epoxy resin was 11, the average number of Si per molecule of product / the average number of epoxy rings per molecule of product was 1.17. It is.

Production Example 4 (Production of methoxy group-containing silane-modified epoxy resin [component (A)])
In the same reactor as in Production Example 1, 2048 g of bisphenol type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 1001”, epoxy equivalent 475), bisphenol type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., product) The name “Epicoat 828”, epoxy equivalent 185), 5184 g and glycidol 546.2 g were charged, and the temperature was raised to 100 ° C. 3960 g of methyltrimethoxysilane partial condensate (the above-mentioned trade name “MTMS-A”, the average number of Si being 3.2) was charged, and the temperature was raised to 100 ° C. Thereafter, 5.66 g of dibutyltin dilaurate was added as a catalyst, and the reaction was allowed to proceed for 11 hours while removing methanol produced by the reaction. The inside of the reaction system was cooled to room temperature to obtain 11300 g of a methoxy group-containing silane-modified epoxy resin (A-4). In addition, the equivalent of the methoxy group of hydrolyzable methoxysilane at the time of charging / the equivalent of the hydroxyl group of the epoxy resin is 13.3, the average number of Si per molecule of product / the average number of epoxy rings per molecule of product is 1. .11.

Production Example 5 (Production of methoxy group-containing silane-modified epoxy resin [component (A)])
In the same reactor as in Production Example 1, bisphenol type epoxy resin (trade name “Epicoat 834”, epoxy equivalent 257) 250 g, 7,8-epoxy-1-octanol (manufactured by Kuraray Co., Ltd., trade name “EOA”) ) 58.2 g and methyltrimethoxysilane partial condensate (the above-mentioned trade name “MTMS-A”, Si average number n is 3.2) were charged, and the temperature was raised to 100 ° C. Thereafter, 0.31 g of dibutyltin dilaurate was added as a catalyst and reacted for 5 hours while removing methanol produced by the reaction. The inside of the reaction system was cooled to room temperature to obtain 500 g of a methoxy group-containing silane-modified epoxy resin (H-5). In addition, the equivalent of the methoxy group of the hydrolyzable methoxysilane / the equivalent of the hydroxyl group of the epoxy resin is 11, the average number of Si per molecule of the product / the average number of epoxy rings per molecule of the product is 1.38. It is.

Production Example 6 (Production of methoxy group-containing silane-modified epoxy resin [component (A)])
In the same reactor as in Production Example 1, 200 g of bisphenol type epoxy resin (trade name “Epicoat 834”, epoxy equivalent 257), 51.8 g of glycidol and tetramethoxysilane partial condensate (trade name “M silicate 51”, The average number n of Si was 4) 232.4 g, and the temperature was raised to 90 ° C. Thereafter, 0.20 g of dibutyltin dilaurate was added as a catalyst, and the reaction was carried out for 10 hours while removing methanol produced by the reaction. The reaction system was cooled to room temperature to obtain 445 g of a methoxy group-containing silane-modified epoxy resin (A-6). In addition, the equivalent of methoxy group of hydrolyzable methoxysilane / equivalent of hydroxyl group of epoxy resin at the time of charging is 20, average number of Si per molecule of product / average number of oxirane rings per molecule of product is 1.31. It is.

Example 1 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-1) obtained in Production Example 1 and toluene silica sol (manufactured by Fuso Chemical Co., Ltd., trade name “Quatron PL-1-Tol) 34.0 g (solid content concentration 40%), 100 g of toluene, and 0.50 g of dibutyltin dilaurate were charged, and the temperature was raised to 120 ° C. The reaction was carried out for 4 hours while removing methanol produced by the reaction, and then the temperature was raised to 130 ° C. to remove toluene. Thereafter, the pressure was reduced to remove volatile components in the system, and 109.5 g of the composite (H-1) was obtained.

Example 2 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-2) obtained in Production Example 2, 20.4 g of the trade name “Quatron PL-1-Tol”, 100 g of toluene, dibutyl 0.10 g of tin dilaurate was charged and the temperature was raised to 120 ° C. The reaction was carried out for 3 hours while removing methanol produced by the reaction, and then the temperature was raised to 130 ° C. to remove toluene. Thereafter, the pressure was reduced to remove the volatile matter in the system, and 106.7 g of the composite (H-2) was obtained.

Example 3 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-3) obtained in Production Example 3, methanol silica sol (manufactured by Fuso Chemical Co., Ltd., trade name “Quatron PL-1-MA”) ”, 50.0 g of solid content concentration 13%) and 0.50 g of dibutyltin dilaurate were charged, and the temperature was raised to 90 ° C. The reaction was carried out for 5 hours while removing methanol produced in the reaction and methanol contained in the silica sol. Thereafter, the pressure was reduced to remove volatile components in the system, and 105.1 g of the composite (H-3) was obtained.

Example 4 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-4) obtained in Production Example 4, methanol silica sol (manufactured by Nissan Chemical Co., Ltd., trade name “Methanol Silica Sol”, solid content) (Concentration was 30%) 27.68 g and 0.05 g of dibutyltin dilaurate were charged, and the temperature was raised to 90 ° C. The reaction was allowed to proceed for 5 hours while removing the methanol produced by the reaction. Thereafter, the pressure was reduced to remove volatile components in the system, and 105.0 g of the composite (H-4) was obtained.

Example 5 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-5) obtained in Production Example 5, 34.1 g of the trade name “Quatron PL-1-Tol”, 100 g of toluene, dibutyl 0.50 g of tin dilaurate was charged and the temperature was raised to 120 ° C. The reaction was carried out for 3 hours while removing methanol produced by the reaction, and then the temperature was raised to 130 ° C. to remove toluene. Thereafter, the pressure was reduced to remove the volatile matter in the system, and 106.8 g of the composite (H-5) was obtained.

Example 6 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-1) obtained in Production Example 1 and aluminum oxide (trade name “UFA-150”, manufactured by Showa Denko KK) 30 .2 g, toluene 100 g, and dibutyltin dilaurate 0.50 g were charged and the temperature was raised to 120 ° C. The reaction was carried out for 4 hours while removing methanol produced by the reaction, and then the temperature was raised to 130 ° C. to remove toluene. Thereafter, the pressure was reduced to remove the volatile matter in the system, and 119.2 g of the composite (H-6) was obtained.

Example 7 (Production of composite)
In the same reactor as in Production Example 1, 100 g of the methoxy group-containing silane-modified epoxy resin (A-6) obtained in Production Example 6, 56.9 g of the above-mentioned trade name “Quatron PL-1-Tol”, 100 g of toluene, dibutyl 0.50 g of tin dilaurate was charged and the temperature was raised to 120 ° C. The reaction was carried out for 3 hours while removing methanol produced by the reaction, and then the temperature was raised to 130 ° C. to remove toluene. Thereafter, the pressure was reduced to remove the volatile matter in the system, and 114.2 g of the composite (H-7) was obtained.

Example 8 (Preparation of complex dispersion)
45 g of a 50% MEK solution of phenol novolac resin (manufactured by Arakawa Chemical Industries, Ltd., trade name “TAMANOR 759, phenol equivalent 106”) and 100 g of MEK were added to 100 g of the composite (H-1) obtained in Example 1. In addition, a composite dispersion was prepared.

Example 9 (Preparation of complex dispersion)
To 100 g of the composite (H-2) obtained in Example 2, 5 g of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name “2E4MZ”) and 100 g of MEK were added, and the composite dispersion was added. Was prepared.

Example 10 (Preparation of complex dispersion)
14 g of pyromellitic acid was added to 100 g of the composite (H-2) obtained in Example 2 to prepare a composite dispersion.

Comparative Example 1 (Preparation of comparative composition)
A comparative epoxy resin composition was prepared by adding 34 g of a 50% MEK solution of phenol novolac resin (the trade name “Tamanol 759”) and 100 g of MEK to 100 g of the bisphenol A type epoxy resin (the trade name “Epicoat 1001”).

Comparative Example 2 (Preparation of comparative composition)
To 100 g of the methoxy group-containing silane-modified epoxy resin (A-1) obtained in Production Example 1, 50 g of a 50% MEK solution of phenol novolac resin (trade name “Tamanol 759”), 2 g of tin octylate, and 100 g of MEK were added. A comparative epoxy resin composition was prepared.

Comparative Example 3 (Preparation of comparative composition)
5 g of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name “2E4MZ”) with respect to 100 g of the methoxy group-containing silane-modified epoxy resin (A-1) obtained in Production Example 1, tin octylate 2 g and MEK 100 g were added to prepare a comparative epoxy resin composition.

(Performance evaluation)
1. Appearance (foaming, cracking, warping) evaluation of cured film 2 g of each of the various composite dispersions obtained in Examples 8 to 10 and various comparative dispersions obtained in Comparative Examples 1 to 3 Were cast in an aluminum cup (5 cm in diameter) and uniformly cast, and then cured by heating at 90 ° C. for 30 minutes and further at 170 ° C. for 2 hours. Subsequently, these cured films were allowed to stand for 48 hours to obtain a cured film having a thickness of about 200 μm. Each cured film was evaluated according to the following criteria. The results are shown in Table 1.
Criteria for foam evaluation ○: No foaming. X: There is foaming.
Criteria for cracking ○: No cracking or warping. X: There exists a crack or curvature.

2. Scratch resistance In the previous section, the dispersion was applied to a glass plate using a bar coater instead of an aluminum cup as a base material, and heat-cured under the same conditions. A cured film was obtained. Using each of the cured films, a pencil scratch test was performed according to the paint general test method of JIS K-5400. The results are shown in Table 1.

  As is clear from Table 1, in the cured products using the composites and dispersions obtained in the examples, no foaming, cracking, or warping occurred regardless of the thickness of 200 μm. Moreover, the hardened | cured material obtained in the said Examples 8-10 was able to provide the cured film of high hardness generally. On the other hand, the cured product obtained from Comparative Example 1 did not crack or warp, but had a low hardness. In addition, the cured products obtained from Comparative Examples 2 and 3 had high hardness, but foaming and warping occurred.

3. Heat resistance Each cured film obtained in the same manner as in item 1 was cut into 5 mm × 25 mm, and viscoelasticity measuring instrument (manufactured by Rheology, trade name “DVE-V4”, measurement condition amplitude 1 μm, vibration frequency 10 Hz, slope The dynamic storage elastic modulus E ′ and Tan δ were measured using 3 ° C./min) to evaluate the heat resistance. The measurement results are shown in FIG.

  As is clear from FIG. 1, in Comparative Example 1, the cured film has a storage elastic modulus that is greatly reduced at around 90 ° C., whereas in Comparative Example 2 and Example 5, the storage elastic modulus of the cured film is low. It is recognized that both of them have excellent heat resistance, not rapidly decreasing.

  It is a heat resistance measurement result of Example 8, Comparative Example 1, and Comparative Example 2.

Claims (11)

  An alkoxy group-containing silane-modified epoxy resin (A) obtained by subjecting a bisphenol-type epoxy resin (a1) and a hydrolyzable alkoxysilane partial condensate (a2) to a dealcoholization condensation reaction and metal oxide particles (B), A method for producing a composite comprising heating under substantially anhydrous conditions to cause a dealcoholization condensation reaction between an alkoxy group in (A) and a hydroxyl group present on the surface of (B).   The method for producing a composite according to claim 1, wherein (A) comprises epoxy alcohol (a3) as an additional component.   The method for producing a composite according to claim 1 or 2, wherein (a1) is a bisphenol A type epoxy resin. (A2) is represented by the following general formula:

4. In the formula, R ¹ represents a methyl group or a methoxy group, and q is 1 to 7, and is represented by poly (tetramethoxysilane) or poly (methyltrimethoxysilane). A method for producing the composite according to claim 1. (A3) is represented by the following general formula:

The manufacturing method of the composite_body | complex in any one of Claims 2-4 represented by (In formula, p is 1-10).   Said (B) is a thing with a particle size of 5-100 nm, The manufacturing method of the composite_body | complex in any one of Claims 1-5.   The use ratio of (A) and (B) is such that [number of moles of hydroxyl group of (B) / number of moles of alkoxy group of (A)] (molar ratio) is 0.5 to 3.0. The manufacturing method of the composite_body | complex in any one of 1-6.   The method for producing a composite according to any one of claims 1 to 7, wherein the metal oxide is at least one selected from the group consisting of silicon oxide, titanium oxide, tin oxide, aluminum oxide, zirconia oxide and zinc oxide.   A composite obtained by the production method according to claim 1.   10. A composite according to claim 9, at least one dispersion medium selected from the group consisting of a liquid epoxy resin, a reactive diluent and an organic solvent, and a curing agent for epoxy resin or an epoxy group ring-opening polymerization catalyst. A composite dispersion characterized by   A complex cured product obtained by curing the complex according to claim 9 or the complex dispersion according to claim 10.

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