TW201434943A - Epoxy resin composition and condensate - Google Patents

Abstract

The present invention provides an epoxy resin composition and a condensate which guarantee the fire resistance by non-halogen, have excellent performances, such as low dielectric property, fire resistance, etc., and are useful for lamination, forming, injection molding and adhesion. The epoxy resin composition comprises an epoxy resin, a curing agent and filling materials, wherein the epoxy resin comprises a p-containing epoxy resin component of which the phosphorus-containing ratio is 1.0 to 6.0 %, and the curing agent contains a polyhydroxy resin represented by formula (1), so that an epoxy resin condensate is obtained by curing the epoxy resin composition.

Description

Epoxy resin composition and hardened material

The present invention relates to an epoxy resin composition and a cured product which are excellent in low dielectric and flame retardancy and also excellent in adhesion.

In recent years, in particular, with the development of the field of advanced materials, there is a demand for the development of higher performance basic resins. For example, in the field of semiconductor sealing, in recent years, in order to make the package thinner and larger in size in response to high-density mounting, and the surface mounting method has become popular, the problem of cracking of the package has been deepened, so that it is strongly required to upgrade the basic resin. Moisture resistance, heat resistance, adhesion to a metal substrate, and the like. In addition, in the field of printed wiring boards, in recent years, in order to process a large amount of information at a high speed, multilayering, thinning, and fine pitch of circuits have been performed. However, in order to realize high-speed processing, wiring materials having more excellent dielectric characteristics are required. Further, in order to reduce the environmental load, the action of removing the halogen-based flame retardant is started, so that a basic resin having a more excellent flame retardancy is required.

A countermeasure for improving the flame retardancy without using a halogen-based flame retardant, such as a phosphorus-containing epoxy resin composition disclosed in Patent Document 1 and Patent Document 2, wherein when it is found to be a matrix resin of a laminate, it is not drop Low insulation reliability provides excellent flame retardancy. However, in the epoxy resin containing phosphorus, the dielectric properties due to the polarization structure of the phosphate structure and the hydroxypropyl group formed during curing due to low epoxy equivalent are not obtained.

Although the prior art Patent Document 3 discloses an epoxy resin composition containing a styrenated phenol novolac type epoxy resin, the invention is directed to improving low water absorption and low stress, and is not flame retardant.

For example, the styrenated phenol novolak type epoxy resin disclosed in Patent Document 4 and the epoxy resin composition containing a styrenated phenol novolak resin are exemplified, but it is difficult to use a halogen-based resin. The technique of imparting flame retardancy to a fuel, and the flame retardancy and dielectric properties cannot be established.

Further, Patent Document 5 discloses that an epoxy resin composition containing a styrene-modified phenol novolac epoxy resin and a phosphorus-containing epoxy resin can improve dielectric properties and flame retardancy, but the flame retardancy is still insufficient. The electrical characteristics are also deteriorated by the addition of the epoxy resin containing phosphorus, so that the flame retardancy and the dielectric properties are required to stand.

Patent Document 6 discloses an epoxy resin composition containing an epoxy resin and a styrene-modified phenol novolak resin as a curing agent. However, there is no review of the epoxy resin containing phosphorus, and the effect thereof is not disclosed. Enough insight.

Further, Patent Document 7 discloses an epoxy resin containing a naphthol and a curing agent to obtain a high heat resistance and a low water absorption property, but the dielectric properties and flame retardancy are not reviewed.

Prior technical literature Patent literature

[Patent Document 1] JP-A-11-166035

[Patent Document 2] Japanese Patent Publication No. 11-279258

[Patent Document 3] Japanese Patent Publication No. 5-140265

[Patent Document 4] Japanese Patent Publication No. 08-165328

[Patent Document 5] JP-A-2012-82250

[Patent Document 6] WO 2012/043213

[Patent Document 7] Japanese Patent Publication No. 03-043412

Summary of invention

Therefore, an object of the present invention is to provide an epoxy which is excellent in low dielectricity, flame retardancy, and the like while ensuring flame retardancy under a non-halogen system, and is suitable for lamination, molding, casting, and the like. Resin composition and cured product thereof.

That is, the epoxy resin composition of the present invention is characterized in that it contains an epoxy resin and a hardener, or the epoxy resin composition of the filler and the filler contains a phosphorus content of 1.0 to 6.0 as an epoxy resin component. weight% The phosphorus-containing epoxy resin and the polyvalent hydroxy resin represented by the following general formula (1) used as a hardener component.

(wherein A represents a benzene ring or a naphthalene ring, Z represents CH ₂ or a structure represented by the following general formula (2), R represents hydrogen, or a hydrocarbon group having 1 to 14 carbon atoms which may contain oxygen, and R' represents hydrogen Or a hydrocarbon group having 1 to 6 carbon atoms, n represents the number from 0 to 20, p represents the number from 0.1 to 6, but the total carbon number of A+R is 9 or more, and when all A is a naphthalene ring, at least one Z is General formula (2)).

(wherein R and p are synonymous with the general formula (1)).

The epoxy resin composition preferably has at least one of the following.

1) The hardener component is a polyvalent hydroxy resin represented by the following general formula (3), (wherein R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents a substituent represented by the following general formula (4), n represents a number of 1 to 20, and p represents a number of 0.1 to 2.5) (wherein R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms).

2) The epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and a phosphorus compound represented by the general formula (5) and/or the general formula (7). (b) a phosphorus-containing epoxy resin obtained by reacting an epoxy group with a reactive starting material, (wherein X represents hydrogen or a group represented by formula (6), q represents 0 or 1, and R ₄ and R ₅ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₄ and R ₅ may be bonded and phosphorus Atom and oxygen atoms together form a ring) (Y represents a aryl group with a carbon number of 6 to 20) (wherein, X represents hydrogen or a group represented by formula (6), r represents 0 or 1, and R ₆ and R ₇ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₆ and R ₇ may be bonded and phosphorus The atoms and oxygen atoms together form a ring).

3) The epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and a phosphorus compound represented by the general formula (5) and/or the general formula (7) ( b) a phosphorus-containing epoxy resin obtained by the reaction, the epoxy equivalent of the phosphorus-containing epoxy resin being in the range of 50 to 95% of the theoretical epoxy equivalent (T) obtained by the following formula (8), T =[(a1)+(b1)]/(AB) (8) wherein (a1) is the amount (g) of the epoxy resin (a), and (b1) is the amount (g) of the phosphorus compound (b) , A is the value obtained by the formula (9), and B is the value obtained by the formula (10).

A=(a1)/ epoxy equivalent of epoxy resin (9)

B=(b1)/Active hydrogen equivalent of phosphorus compounds (10)

4) The epoxy resin component is further composed of 5 to 50% by weight of the epoxy resin represented by the general formula (11). (wherein G represents a glycidyl group, and R ₁ , R ₂ , n and p are synonymous with the general formula (3)).

5) The hardener component is a polyvalent hydroxy resin represented by the following general formula (12), (wherein R ₈ represents hydrogen or a hydrocarbon group having 1 to 9 carbon atoms which may contain oxygen, n represents a number of 0 to 20, and p represents a number of 3 to 6).

6) The epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and a phosphorus compound represented by the general formula (13) and/or the general formula (15) ( b) the phosphorus-containing epoxy resin obtained by the reaction, (wherein X is hydrogen or a group represented by formula (14), q represents 0 or 1, and R ₄ and R ₅ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₄ and R ₅ may be bonded and phosphorus Atom and oxygen atoms together form a ring) (Y represents a aryl group with a carbon number of 6 to 20) (wherein X is hydrogen or a group represented by formula (14), r represents 0 or 1, and R ₆ and R ₇ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₆ and R ₇ may be bonded and phosphorus The atoms and oxygen atoms together form a ring).

7) The epoxy equivalent of the epoxy resin containing phosphorus is in the range of 50 to 95% by weight of the theoretical epoxy equivalent (T) obtained by the following formula (16), T = [(a1) + (b1)] / (AB) (16) wherein (a1) is the weight (g) of the epoxy resin (a), (b1) is the weight (g) of the phosphorus compound (b), and A is represented by the following formula (17) The value to be obtained, B is a value obtained by the following formula (18).

A=(a1)/ epoxy equivalent of epoxy resin (17)

B=(b1)/Active hydrogen equivalent of phosphorus compounds (18)

8) The epoxy resin is an epoxy resin represented by the following general formula (19), which further contains 5 to 50% by weight of the total epoxy resin and has an epoxy equivalent of 200 g/eq or more. (wherein G represents a glycidyl group, R ₉ represents hydrogen or a hydrocarbon group having 1 to 9 carbon atoms, and m represents a number of 1 to 20).

9) The filler is fibrous glass.

Further, the present invention is an epoxy resin cured product obtained by curing the above epoxy resin composition.

The epoxy resin composition of the present invention contains an epoxy resin containing phosphorus, a polyvalent hydroxy resin having a specific structure, and a filler as essential components, and therefore has at least excellent low dielectric and flame retardancy, and a cured product of adhesion. Therefore, it is suitable for use as an electronic material such as a resin composition for a printed circuit board or a resin composition for a sealing material for an electronic component.

Form of implementing the invention

The present invention is characterized in that an epoxy resin composition comprising an epoxy resin and a hardener, or an epoxy resin, a hardener and a filler is used as an epoxy resin component, and the phosphorus content is 1.0 to 6.0 weight. A phosphorus-containing epoxy resin and an epoxy resin composition of a polyvalent hydroxy resin represented by the following general formula (1) used as a hardener component. Moreover, the epoxy resin composition according to the present invention is a cured product which can provide at least an excellent low dielectric property, flame retardancy, and adhesion, and is suitable for a resin composition for a printed circuit board or a sealing material for an electronic component. The use of the electronic material such as the resin composition is preferably in accordance with the following two embodiments depending on the hardener component to be used. Each of the epoxy resin compositions of the present invention will be specifically described in the following first embodiment and second embodiment. Also, the present invention The scope is not limited to the embodiments.

(wherein A represents a benzene ring or a naphthalene ring, Z represents CH ₂ or a structure represented by the following general formula (2), R represents hydrogen, or a hydrocarbon group having 1 to 14 carbon atoms which may contain oxygen, and R' represents hydrogen Or a hydrocarbon group having 1 to 6 carbon atoms, n represents the number from 0 to 20, p represents the number from 0.1 to 6, but the total carbon number of A+R is 9 or more, and when all A is a naphthalene ring, at least one Z is generally Formula (2)).

(wherein R and p are synonymous with the general formula (1)).

[First embodiment]

In the epoxy resin composition of the first embodiment of the present invention, an epoxy resin and a curing agent represented by the general formula (3) are essential components. Preferably, the epoxy resin, the hardener represented by the general formula (3), and the filler are essential components. The content of the essential components is 50% by weight or more, preferably 80% by weight or more, and more preferably 95% by weight or more.

First, a polyvalent hydroxy resin (also referred to as StPN) represented by the general formula (3) used as a curing agent component in the epoxy resin composition of the first embodiment of the present invention will be described. The polyvalent hydroxy resin can be obtained by an addition reaction of a polyvalent hydroxy compound (also referred to as a polyvalent hydroxy compound (20)) represented by the following general formula (20) with a styrene. The general formula (3) has the same meaning as the symbol common to the general formula (20). In the general formula (3), p represents a number from 0.1 to 2.5, which is an average number (number average) of R ₂ per one benzene ring.

The StPN represented by the general formula (3) is a polyvalent hydroxy resin to which styrene is added. StPN can be arbitrarily adjusted by adjusting the hydroxyl equivalent by adding styrene to the benzene ring of the polyvalent hydroxy compound (20). The additional styrene means that the hydrogen of the benzene ring of the polyvalent hydroxy compound (20) and the substituent represented by the formula (4) (also referred to as α-methylbenzyl or styryl) are substituted. That is, in the cured epoxy resin, the hydroxypropyl group formed by the reaction of the epoxy group and the hydroxyl group is flammable, but when the hydroxy group is added to the polyvalent hydroxy compound to increase the hydroxyl group equivalent, the epoxy group can be reduced. The proportion of aliphatic carbon in the flammable component is found to be highly flame retardant. Further, by adding aromatic styrene, the aromaticity of the polyvalent hydroxy resin can be further enhanced, so that the moisture resistance can be effectively improved in addition to the flame retardancy.

Further, by using the polyvalent hydroxy compound of the general formula (3), the hydroxypropyl group of the polar group in the cured epoxy resin can be reduced, and therefore, in addition to flame retardancy, Moisture resistance can also effectively reduce the dielectric constant and dielectric loss tangent.

The method for producing StPN used in the present invention is not limited, but a method of reacting a polyvalent hydroxy compound (20) with a styrene is preferred. At this time, the ratio of the polyvalent hydroxy compound (20) to the styrene is used in consideration of the balance between the flame retardancy and the hardenability of the cured product obtained, and the ratio of the styrene to the polyvalent hydroxy compound 1 mol. It is preferably 0.2 to 2.5 m, and preferably 0.6 to 2.0 m, more preferably 0.9 to 1.5 m. When the amount is less than this range, the properties of the polyvalent hydroxy compound of the raw material cannot be improved and the original state is maintained. When the content is more than this range, the functional group density is excessively lowered and the curability is lowered.

Further, the softening point of StPN may be 40 to 130 ° C, preferably 50 to 100 ° C. The softening point means a softening point measured according to the ring method of JIS-K-2207. Below this value, there is a blocking problem when stored, and when it is higher than this value, there is a problem of kneading and formability when the epoxy resin composition is adjusted.

In the general formula (4), R ₃ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, but is preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen. The R ₃ may be determined depending on the styrene used as the starting material for the reaction.

In the general formulas (3) and (20), n represents a number from 1 to 20, preferably an average (number average) of from 1.5 to 7.0.

The polyvalent hydroxy compound (20) is obtained by reacting a phenol with formalin. The phenol is a phenol substituted with a phenol or a hydrocarbon group having 1 to 6 carbon atoms, but is preferably a phenol or a phenol substituted with an alkyl group having 1 to 4 carbon atoms, more preferably phenol. When phenol is used, phenol may contain a small amount of other phenols. Share. Other phenolic components such as o-cresol, m-cresol, p-cresol, ethyl phenol, isopropyl phenol, tert-butyl phenol, allyl phenol, phenyl phenol, 2 , 6-xylenol, 2,6-diethylphenol, hydroquinone, resorcinol, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1, 6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, and the like. These phenols or naphthols may contain two or more types.

The styrene used for the reaction with the polyvalent hydroxy compound is styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms, but is preferably styrene. The styrene may contain a small amount of other reaction components, and when the styrene is styrene, other reaction components such as α-methylstyrene, divinylbenzene, anthracene, benzofuran, and benzo may be contained. A component containing a non-saturated bond such as thiophene, anthracene or vinylnaphthalene, and the polyvalent hydroxy resin obtained at this time contains a compound on the aromatic ring substituted by the group formed.

The reaction of the polyvalent hydroxy compound with the styrene can be carried out in the presence of an acid catalyst, and the amount of the catalyst used is in the range of 10 to 1000 ppm, preferably in the range of 100 to 500 ppm. When the amount is more than this amount, the methyl crosslinkage bond of the phenol novolak is easily cleaved, and the monovalent phenol component by-produced by the cracking reaction lowers the hardenability and heat resistance. In addition, less than this amount lowers the reactivity, and a large amount of unreacted styrene monomer remains.

The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids. For example, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid or diethylsulfonic acid, or zinc chloride, aluminum chloride or chlorine. Lewis acid or ion exchange resin such as iron or boron trifluoride, activated clay, ceria-aluminum, zeolite, etc. Solid acid and the like.

Further, the reaction is generally carried out for 1 to 20 hours. Further, an alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve may be used for the reaction, or acetone, methyl ethyl ketone or methyl isobutyl group. As a solvent, an ketone such as a ketone, a dimethyl ether, a diethyl ether, a diisopropyl ether, an ether such as tetrahydrofuran or a dioxane, or an aromatic compound such as benzene, toluene, chlorobenzene or dichlorobenzene. use.

The specific method for carrying out the reaction is generally a method in which the reaction is carried out by directly adding the raw materials at a certain temperature, or after the polyvalent hydroxy compound and the catalyst are placed, and the styrene is dropped at a constant temperature. The dropping time at this time is preferably 5 hours or less, and is usually 1 to 10 hours. When a solvent is used after the reaction, the solvent used in the present invention can be obtained by removing the solvent component after removing the solvent component, and if necessary, the target product can be obtained by direct heating and discharging.

Next, a phosphorus-containing epoxy resin used in the epoxy resin composition of the first embodiment of the present invention will be described. The phosphorus content of the phosphorus-containing epoxy resin (P/phosphorus-containing epoxy resin) is 1.0 to 5.0% by weight.

The method for producing an epoxy resin containing phosphorus is known from the above-mentioned patent documents and the like. The production method is not limited, but a preferred epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and is represented by the above general formula (5) and/or general formula (7). The phosphorus compound (b) or a phosphorus-containing epoxy resin obtained by reacting an epoxy group containing the same with a reactive material. An epoxy group other than the phosphorus compound (b) and a reactive raw material such as a compound having a phenolic hydroxyl group, an amine group, or an acid anhydride group Wait.

In the general formula (5), X is hydrogen or a group represented by the formula (6), q is 0 or 1, and R ₄ and R _{5 are} independently a hydrocarbon group having 1 to 6 carbon atoms, but R ₄ and R ₅ may be bonded. At the same time, the phosphorus atom forms a ring with the oxygen atom. When the ring is formed, the two ends of the bond -R ₄ -P-(O)qR ₅ - form a ring. In the formula (6), Y is an exoaryl group having 6 to 20 carbon atoms.

In the general formula (7), X is hydrogen or a group represented by the above formula (6), r is 0 or 1, and R ₆ and R _{7 are} independently a hydrocarbon group having 1 to 6 carbon atoms, but R ₆ and R ₇ may be bonded. The junction simultaneously forms a ring of phosphorus atoms with oxygen atoms.

Several representative reaction formulas of epoxy-containing epoxy resins derived from epoxy resins and phosphorus compounds are described below.

The phosphorus compound represented by the above general formula (5) and/or the general formula (7) is incompatible with a general epoxy resin and is difficult to be uniformly dispersed in an epoxy resin, so that reaction with an epoxy resin improves compatibility and pursues The uniformity of the physical properties of the hardened material. Further, in addition to the phosphorus compound (b), a polyfunctional compound which can be reacted with an epoxy resin can be used, and the chain length of the epoxy resin portion can be extended to obtain a phosphorus-containing epoxy resin which is more excellent in compatibility.

More preferably, the epoxy equivalent of the phosphorus-containing epoxy resin is in the range of 50% to 95% of the theoretical epoxy equivalent (T) obtained by the above formula (8).

In the general formula (8), (a1) is the amount of the epoxy resin (a) (g) (b1) is the amount (g) of the phosphorus compound (b). A is a value obtained by the formula (9), and B is a value obtained by the formula (10). The unit of the epoxy equivalent and the active hydrogen equivalent at this time is g/eq.

When a polyfunctional compound which can be reacted with an epoxy resin is used in addition to the phosphorus compound (b), the amount and the hydroxyl equivalent are based on the amount of the raw material containing the phosphorus compound (b) and the total functional group in the raw material (having an epoxy resin) The equivalent of the reactive functional group is calculated by the formula (8). For example, when the phenol compound is a hydroxyl group equivalent, an acid anhydride is an acid anhydride equivalent, and an amine compound or a phosphorus compound having a hydrogen directly bonded to a phosphorus atom is an active hydrogen equivalent.

Epoxy resin used in the manufacture of epoxy resin containing epoxy (a), such as Yeppes YD-128, Yeppes YD-8125 (bisphenol A epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Yebo YDF-170, Yeppes YDF-8170 (bisphenol F epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YSLV-80XY (tetramethyl bisphenol F epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) Yeppey YDC-1312 (hydroquinone epoxy resin), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), YeppeN YDPN-638 (Nippon Steel Co., Ltd. phenol novolac Epoxy resin), YeppeN Y-CN-701 (Nippon Steel Chemical Co., Ltd. cresol novolac type epoxy resin), Yeppes TX-1210 (Nippon Steel Chemical Co., Ltd. replaced phenolic epoxy resin ), Yeppes ZX-1201 (bisphenol bismuth epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), TX-0710 (bisphenol S type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Yippico EXA- 1515 (bisphenol S type epoxy resin manufactured by Dainippon Chemical Industry Co., Ltd.), NC-3000 (biphenyl aralkyl phenol type manufactured by Nippon Kasei Co., Ltd.) Epoxy resin), Yeppes ZX-1355, Yeppes ZX-1711 (naphthalene glycol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Yeppes ESN-155 (Nippon Steel Chemical Co., Ltd. -naphthol aralkyl type epoxy resin), Yeppes ESN-355, Yeppes ESN-375 (Ninatron Chemical Co., Ltd. bisphthol aralkyl type epoxy resin), Yebbert ESN 475V , Yeppes ESN-485 (α-naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPPN-501H (triphenylmethane epoxy resin manufactured by Nippon Kagaku Co., Ltd.), Smith耶 TMH-574 (Triphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.), YSLV-120TE (disulfide epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Yeppes ZX-1684 (Nippon Steel Chemical Co., Ltd. made resorcinol type epoxy resin), Danaco EX-201 (sodium succinyl epoxy resin manufactured by Nagase Co., Ltd.), and Yippico HP-7200H (dicyclopentane bis produced by DIC Corporation) Epoxy resin produced from a phenolic compound of a polyvalent phenol resin and an epihalohydrin, such as an olefinic epoxy resin, TX-0929, TX-0934, and TX-1032 (alkane diol type manufactured by Nippon Steel Chemical Co., Ltd.) Epoxy tree Epoxy resin made from ethanol compound and epichlorohydrin, Xerogi 2021 (alicyclic epoxy resin manufactured by Dyson Chemical Industry Co., Ltd.), Yeppeh YH-434 (Nippon Steel) Epoxy resin made of amine compound and epihalohydrin, etc., jER 630 (aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation), etc., manufactured by Chemicals Co., Ltd., diaminodiphenylmethane tetraepoxypropylamine) , yoke FX-289B, yoke FX-305, TX-0932A (Nippon Steel Chemical Co., Ltd. containing phosphorus epoxy resin) and other epoxy resins and phosphorus-containing phenol compounds modified by the modifier obtained Phosphorus-containing epoxy resin, urethane modified epoxy resin, The epoxy resin containing an oxazolinone ring is not limited to these. Further, these epoxy resins may be used singly or in combination of two or more.

The raw material (referred to as a reactive raw material) containing the phosphorus compound (b) represented by the general formula (5) and/or the general formula (7) may contain another phosphorus compound which is reactive with the epoxy resin. By containing a phosphorus compound having a function as a chain length extender, the chain length can be elongated to increase the compatibility with the epoxy. Specifically, for example, 10-(2,5-dihydroxyphenyl)-10H-9-oxo-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ) , 10-(1,4-dimethoxynaphthalene)-10H-9-oxo-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA-NQ), diphenylphosphinylhydroquinone ( Made by Beixing Chemical Industry Co., Ltd., trade name PPQ), diphenylphosphinyl-1,4-dimethoxynaphthalene, 1,4-cyclodecylphosphinyl-1,4-phenylene glycol (Japan) Chemical Industry Co., Ltd., trade name CPHO-HQ), 1,5-cyclooctyl octylphosphinyl-1,4-phenylene glycol (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ), etc. Phosphorus phenols, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA) or diphenylphosphine, etc., have direct bonding to phosphorus atoms. The phosphorus compound of active hydrogen is not limited thereto. Further, these phosphorus compounds may be used in combination of two or more kinds.

Further, the phosphorus-containing phenol compound may be directly derived from 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA) or diphenylphosphine. A phosphorus compound bonded to an active hydrogen of a phosphorus atom is obtained by reacting with an anthracene such as 1,4-benzoquinone or 1,4-naphthoquinone. HCA-HQ can be used with special opening Kai 60-126293, HCA-NQ can be used Sho 61-236787, PPQ can use the synthesis method shown in zh. Obshch. Khim, 42 (11), pp. 2415-2418 (1972), but is not limited thereto, and a known conventional method can be used.

Further, the compounds having a functional group reactive with an epoxy group other than the phosphorus-containing compound are hydroxybenzenes such as catechol, resorcin, and hydroquinone, and diphenols. Dinaphthols, trisphenols, bisphenol A, bisphenol F, bisphenol S, sinol BRG-555 (made by Showa Denko KK, phenol novolac resin), cresol novolac resin, alkyl phenol novolac Resin, aralkyl phenol novolak resin, phenol novolak resin containing triazine ring, biphenyl aralkyl phenol resin, Regit TPM-100 (manufactured by Qunrong Chemical Industry Co., Ltd., trihydroxyphenylmethane type phenolic) a compound having two or more phenolic hydroxyl groups in one molecule such as a varnish resin or an aralkyl naphthalenediol resin; an anthracene adipic acid; an anthraquinone azelate; an imidazole compound; Its salts, dicyandiamide, aminobenzoic acid esters, di-ethyltriamine, tri-ethylidene tetraamine, tetra-ethylhexamine, m-xylenediamine, isophorone diamine Alicyclic amines, diaminodiphenylmethane, diaminodiphenyl hydrazine, diamine Aromatic amines such as ethyl ethylbenzene, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, A Two or more kinds of these may be used as an acid anhydride such as a bare acid anhydride. The amount of the compound to be used is preferably 0.5 equivalent or less, more preferably 0.2 equivalent or less, based on 1 equivalent of the epoxy group in the epoxy resin to be used. Further, when these compounds are used in combination with a compound containing phosphorus, the equivalent amount of the reactive groups of the compounds is also included in the formula (10). The hydroxyl equivalent of the phosphorus compound is calculated, and the epoxy equivalent is preferably in the range of 50 to 95%.

The range in which the epoxy resin is 50 to 95% of the theoretical epoxy equivalent (T) means that the functional group of the reactive raw material may remain in the reaction between the epoxy resin (a) and the raw material containing the phosphorus compound (b). This residual function is based on the hardening reaction which reacts with the epoxy group and the epoxy group to find an excellent hardened physical property.

Further, the epoxy resin containing phosphorus is obtained by reacting 0.10 equivalent to 0.94 equivalent of a reactive functional group of a reactive raw material with respect to 1 equivalent of the epoxy group of the epoxy resin (a), preferably 0.20 equivalent to 0.70 equivalents, more preferably in the range of 0.20 equivalents to 0.60 equivalents. When the compound (b) having a reactive functional group is less than 0.10 equivalent, the flame retardancy is insufficient, and when it exceeds 0.94 equivalent, the paint viscosity of the phosphorus-containing epoxy resin obtained by the reaction is increased.

The epoxy equivalent of the phosphorus-containing epoxy resin is preferably in the range of 50% to 95% of the theoretical epoxy equivalent (T), preferably in the range of 70% to 95%, more preferably 75% to 90%. range. When it is less than 50%, a large amount of a flame-retardant phenol compound containing phosphorus is left, and solvent solubility is lacking. When it is more than 95%, the viscosity when used as an epoxy resin paint is increased to affect workability. When the theoretical epoxy equivalent (T) is in the range of 50% to 90%, the reactive functional group derived from the reactive raw material remains, and it acts as a hardener component in the hardening reaction to contribute to the reaction.

The reaction temperature for the reaction for producing the epoxy resin containing phosphorus is preferably from 100 ° C to 250 ° C, more preferably from 130 ° C to 180 ° C. Below 100 ° C The reaction is obviously slowed down, and it is difficult to control the reaction in the range of 50% to 95% of the theoretical epoxy equivalent at 250 ° C or higher.

Further, a reaction for producing an epoxy resin containing phosphorus can be used, and if necessary, a reaction catalyst for promoting the reaction can be used. Catalysts which can be used, such as triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, etc., n-butyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide a quaternary ammonium salt such as a quaternary phosphonium salt such as a sulfonium salt, a 2-methyl-4-methylimidazole or a 2-phenylimidazole, a tetramethylammonium chloride or a tetraethylammonium bromide; A known conventional catalyst such as a tertiary amine such as triethylamine or benzyldimethylamine is not limited thereto. Preferred catalysts such as phosphines, particularly preferred catalysts, are phosphines substituted with hydrocarbyl groups which may contain oxygen. The amount of the catalyst used is preferably in the range of 0.005% to 1% based on the reactive raw material.

The reaction of the epoxy resin with the reactive starting material can be carried out in a solvent-free or solvent-free manner, and is preferably carried out in a solvent in an aprotic solvent, such as toluene, xylene, methanol, ethanol, 2-butoxyethanol. , dialkyl ether, glycol ether, propylene glycol monomethyl ether, dioxane, and the like. These reaction solvents may be used singly or in combination of two or more kinds. The amount of the reaction solvent used is preferably 50% or less of the total weight of the reactants.

Further, the reaction for producing the epoxy resin containing phosphorus can be carried out by adjusting the amount of the catalyst so that the epoxy equivalent is in the range of 50% to 95% of the theoretical epoxy equivalent, and the reaction temperature can be adjusted at the same time. A known conventional production method such as a reaction, but is not limited thereto.

The epoxy resin composition according to the first embodiment of the present invention contains the above-mentioned phosphorus-containing epoxy resin as an epoxy resin. It must be used as a component, and the polyvalent hydroxy resin of the general formula (3) used as a hardener, and a filler as an essential component, and if necessary, may contain other epoxy resins, epoxy resin hardeners, hardening accelerators, Filler, etc.

The epoxy resin used in the epoxy resin composition of the first embodiment of the present invention contains the phosphorus-containing epoxy resin as an essential component, but may contain the phosphorus-containing epoxy resin, and the other properties are not impaired. Epoxy resin. The other epoxy resin is preferably a bifunctional or higher epoxy resin, for example, an epoxy resin for synthesizing a phosphorus-containing epoxy resin, but is not limited thereto. Further, these epoxy resins may be used in combination of two or more kinds. In the all-epoxy resin component, the content of the phosphorus-containing epoxy resin is 50% by weight or more, preferably 70% by weight or more.

The amount of the curing agent used in the epoxy resin composition of the first embodiment of the present invention is preferably in the range of 0.5 to 1.3 equivalents based on 1 equivalent of the theoretical epoxy equivalent of the epoxy resin. More preferably 0.7 to 1.1 equivalents. In the total hardener, the content of the polyvalent hydroxy resin of the general formula (3) may be 15% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more.

Further, when the fluidity, the viscosity, and the like are adjusted, a diluent can be used insofar as the physical properties of the epoxy resin composition of the first embodiment of the present invention are not impaired. The diluent is preferably a reactive diluent or a non-reactive diluent. a reactive diluent such as monofunctional glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether or the like, resorcinol glycidyl ether, neopentyl glycol glycidyl ether, 1, Difunctional, glycerol polyglycidyl ether, trimethylolpropane polycondensate such as 6-hexanediol diglycidyl ether A polyfunctional glycidyl ether such as oleyl ether or pentaerythritol polyglycidyl ether. Non-reactive diluents such as benzyl alcohol, butyl diglycol, pine oil, and the like.

Further, in the epoxy resin composition of the first embodiment of the present invention, a curing accelerator may be used as necessary. For example, phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3-(3,4-dichlorodiphenyl)-1 , 1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, and the like. These hardening accelerators vary depending on the type of epoxy resin used, the type of epoxy resin hardener used, the molding method, the curing temperature, and the required characteristics, but the weight is preferably 0.01% to 20% relative to the weight of the epoxy resin. The range of % is more preferably 0.1% to 10%.

In the epoxy resin composition of the first embodiment of the present invention, other thermosetting resin or thermoplastic resin may be added in the range of non-destructive properties. For example, phenol resin, acrylic resin, petroleum resin, enamel resin, coumarone oxime resin, phenoxy ester resin, polyurethane, polyester, polyamine, polyimine, polyamidimide, Polyether phthalimide, polyphenylene ether, modified polyphenylene ether, polyether oxime, polyfluorene, polyetheretherketone, polyphenylene sulfide, polyvinyl formal, etc., but not limited In these.

The filler added to the epoxy resin composition of the present invention is, for example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate. , calcium citrate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, alumina alumina fiber, tantalum carbide fiber, polyester fiber, cellulose Fiber, aromatic polyamide fiber, etc. . These fillers are preferably from 1 to 70% by weight based on the total of the resin composition.

When the epoxy resin composition is used as a plate-like substrate, the filler is preferably a fibrous material from the viewpoints of dimensional stability and bending strength. More preferably, it is a glass fiber substrate obtained by weaving glass fibers in a mesh shape.

The epoxy resin composition according to the first embodiment of the present invention may further contain a decane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a shake imparting agent, a smoothing agent, a flame retardant, and the like, if necessary. Nuclear additives such as pigments. These additives are preferably in the range of 0.01% to 20% by weight based on the resin composition.

The epoxy resin composition of the first embodiment of the present invention can be molded and hardened by the same method as the known epoxy resin composition to obtain a cured product. The molding method and the hardening method may be the same as the known epoxy resin composition, for example, curing at 130 ° C to 200 ° C for 1 hour to 5 hours. Also, it can be used as a paint.

The cured epoxy resin according to the first embodiment of the present invention may be in the form of a laminate, a molded product, a laminate, a coating film, a film, or the like.

[Second embodiment]

In the epoxy resin composition of the second embodiment of the present invention, an epoxy resin and a curing agent represented by the general formula (12) are essential components. Preferably, the epoxy resin, the hardener represented by the general formula (12), and the filler are essential components. In the same manner as the epoxy resin composition of the first embodiment, it is possible to impart a cured product having excellent low dielectric properties, flame retardancy and adhesion, and excellent heat resistance. The content of these essential ingredients is 50% by weight or more, preferably 80% by weight or more, more preferably 95% by weight or more.

Next, a polyvalent hydroxy resin represented by the general formula (12) of the hardener component in the epoxy resin composition of the second embodiment of the present invention will be described. The polyvalent hydroxy resin represented by the general formula (12) is obtained by reacting an aldehyde and a naphthol with a phenol and/or a substituted phenol, for example, as disclosed in Patent Document 5, o-cresol, p-formaldehyde, α - Naphthol is a polyvalent hydroxy resin as a raw material.

The raw material phenol and/or substituted phenol of the polyvalent hydroxy resin represented by the general formula (12) means, for example, phenol, cresol, ethylphenol, xylenol, butylphenol, octylphenol, phenylphenol, The styrenated phenol, cumylphenol, and the like are, but are not limited thereto. Further, these phenols may be used singly or in combination of two or more kinds.

The raw material aldehyde of the polyvalent hydroxy resin represented by the general formula (12) means, for example, formaldehyde or paraformaldehyde, but is not limited thereto. Further, these aldehydes may be used singly or in combination of two or more kinds.

Raw material naphthols of the polyvalent hydroxy resin represented by the general formula (12), such as naphthol, methyl naphthol, dimethyl naphthol, butyl naphthol, benzyl naphthol, and the like, and the like , but not limited to these. Further, these naphthols may be used singly or in combination of two or more kinds.

The method for synthesizing the polyvalent hydroxy resin represented by the general formula (12) is preferably the method described in Patent Document 7, and specifically, the resole phenol resin can be obtained from o-cresol and p-formaldehyde by a metal hydroxide. It is obtained by reacting α-naphthol under an acid catalyst. Further, the obtained polyvalent hydroxy resin The softening point is preferably 100 ° C or more, more preferably 120 ° C or more, and still more preferably 130 ° C or more. When the softening point is lower than 100 ° C, heat resistance and flame retardancy are impaired at the same time.

Next, a phosphorus-containing epoxy resin composition used in the epoxy resin composition of the second embodiment of the present invention will be described. The phosphorus content of the phosphorus-containing epoxy resin (P/phosphorus-containing epoxy resin) is 1.0 to 6.0% by weight.

A method for producing an epoxy resin containing phosphorus can be known from the above-mentioned patent documents and the like. The production method is not limited, but the epoxy resin containing phosphorus is preferably an epoxy resin (a) having two or more epoxy groups in one molecule, and the above general formula (13) and/or general formula (15). A phosphorus-containing epoxy resin obtained by the reaction of the phosphorus compound (b).

If necessary, a phosphorus-containing epoxy resin obtained by reacting the epoxy resin (a) with the phosphorus compound (b) may be used as a raw material (modified agent) which can react with the epoxy group other than the phosphorus compound (b). Upgraded. Specific examples of the raw material to be reacted with the epoxy group include a compound having a phenolic hydroxyl group, an amine group, and an acid anhydride group.

In the general formula (13), X is hydrogen or a group represented by the formula (14), q is 0 or 1, and R ₄ and R _{5 are} independently a hydrocarbon group having 1 to 6 carbon atoms, but R ₄ and R ₅ may be bonded. At the same time, the phosphorus atom and the oxygen atom form a ring. When the ring is formed, a ring is bonded at both ends of -R ₄ -P-(O)-qR ₅ to form a ring. In the formula (14), Y is an exoaryl group having 6 to 20 carbon atoms.

In the general formula (15), X is hydrogen or a group represented by the above formula (14), r is 0 or 1, and R ₆ and R ₇ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₆ and R ₇ may be bonded. The junction forms a ring together with the phosphorus atom and the oxygen atom.

Several representative reaction formulas of epoxy-containing epoxy resins derived from epoxy resins and phosphorus compounds are described below.

The phosphorus compound represented by the above general formula (13) and/or the general formula (15) is difficult to uniformly disperse in the epoxy resin because it is incompatible with a general epoxy resin, and therefore reacts with an epoxy resin in advance to improve compatibility. The uniformity of the physical properties of the hardened material can be obtained. Further, by using a polyfunctional compound which can react with an epoxy resin other than the above-mentioned phosphorus compound (b), the chain length of the epoxy resin portion can be lengthened, and a phosphorus-containing epoxy resin having more excellent compatibility can be obtained.

More preferably, the epoxy equivalent of the epoxy resin containing phosphorus is The range of 50% to 95% of the theoretical epoxy equivalent (T) obtained by the above formula (16). In the formula (16), (a1) is the weight (g) of the epoxy resin (a), and (b1) is the weight (g) of the phosphorus compound (b). Further, A is a value obtained by the equation (17), and B is a value obtained by the equation (18). The unit of the epoxy equivalent and the active hydrogen equivalent at this time is g/eq.

The phosphorus compound (b) is a phosphorus compound represented by the general formula (13) and/or the general formula (15), wherein when X is hydrogen, the active hydrogen which is directly bonded to the phosphorus atom reacts with the epoxy group. Therefore, the active hydrogen equivalent is defined by the number of active hydrogens. Further, when X is a general formula (14), the substance which reacts with the epoxy is a phenolic hydroxyl group, and the active hydrogen equivalent is defined by the number of the active hydroxyl groups.

When a polyfunctional compound which can react with an epoxy resin other than the phosphorus compound (b) is used, the weights and active hydrogen equivalents of the formulae (16) and (18) are obtained by adding the phosphorus compound (b) and the polyfunctional compound in total. The calculation of the formula (16) is carried out by the weight of the raw material and the equivalent of all the functional groups (functional groups reactive toward the epoxy resin) in the raw material. For example, when the polyfunctional compound is a phenol compound, it is a hydroxyl equivalent, an acid anhydride is an acid anhydride equivalent, and an amine compound is an active hydrogen equivalent.

The epoxy resin (a) for producing a phosphorus-containing epoxy resin has two or more epoxy groups in one molecule, and the number of the average functional groups contained in the viewpoint of heat resistance is preferably 2.1 or more. Further, from the viewpoint of flame retardancy, it is preferred to contain more aromatics. Specifically, Yappet YD-128, Yeppes YD-8125 (Nippon Steel Chemical Co., Ltd. bisphenol A epoxy resin), Yeppes YDF-170, Yeppes YDF-8170 (Nippon Steel Chemical shares Company bisphenol F-type epoxy resin), YSLV-80XY (tetramethyl bisphenol F-type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Yeppes YDC-1312 (hydroquinone epoxy resin) , jERYX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), YeppeN YDPN-638 (Nippon Steel Chemical Co., Ltd. phenol novolac type epoxy resin), Yeppen YDCN-701 (Nippon Steel Chemical Co., Ltd. Co., Ltd. cresol novolac type epoxy resin), Yeppes TX-1210 (Nippon Steel Chemical Co., Ltd. replaced phenolic epoxy resin), Yeppes ZX-1201 (Nippon Steel Chemical Co., Ltd. double Phenolphthalein type epoxy resin), TX-0710 (bisphenol S type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Yippik EXA-1515 (bisphenol S type epoxy resin manufactured by Dainippon Chemical Industry Co., Ltd.) , NC-3000 (biphenyl aralkyl phenol type epoxy resin manufactured by Nippon Kasei Co., Ltd.), Yeppes ZX-1355, Yeppes ZX-1711 (nathene glycol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) Resin), Yeppes ESN-155 (N-Nippon Steel Chemical Co., Ltd. β-naphthol aralkyl epoxy resin), Yebéon ESN-355, Yebéon ESN-375 (Nippon Steel Chemical Co., Ltd. Silytical arsenic aralkyl epoxy resin), Yebéon ESN475V, Yepport ESN-485 (α-naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPPN-501H ( Nippon Chemical Co., Ltd. made triphenylmethane type epoxy resin), Smither TMH-574 (Triphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.), YSLV-120TE (made by Nippon Steel Chemical Co., Ltd.) Thioether type epoxy resin), Yeppes ZX-1684 (Nippon Steel Chemical Co., Ltd. made resorcinol type epoxy resin), Tanah's EX-201 (Nagasto Co., Ltd. made resorcinol type epoxy) Resin), Yippico HP-7200H (made by DIC Corporation) Epoxy resin made of naphthol compound and epihalohydrin, polyvalent phenol resin such as dicyclopentadiene type epoxy resin), TX-0929, TX-0934, TX-1032 (Nippon Steel Chemical Co., Ltd. Epoxy resin produced from an ethanol compound and epichlorohydrin, such as an alkylene glycol type epoxy resin, and a sirocco 2021 (aliphatic epoxy resin manufactured by Dychel Chemical Industries, Ltd.), Yebo Epoxy resin, jER 630 (manufactured by Mitsubishi Chemical Corporation), which is made of an amine compound and epihalohydrin, etc., such as YH-434 (diamine diphenylmethane tetraepoxypropylamine manufactured by Nippon Steel Chemical Co., Ltd.) Epoxy resin and phosphorus-containing epoxy resin, yoke FX-289B, yoke FX-305, TX-0932A (epoxy resin containing phosphorus from Nippon Steel Chemical Co., Ltd.) A phosphorus-containing epoxy resin, a urethane-modified epoxy resin, an epoxy resin containing an oxazolinone ring, or the like obtained by a modification of a phenol compound or the like is not limited thereto. Further, these epoxy resins may be used singly or in combination of two or more.

Specific examples of the phosphorus compound (b) represented by the general formula (13) and/or the general formula (15), for example, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (Sanguang Co., Ltd.) a phosphorus compound having a living hydrogen group directly bonded to a phosphorus atom, such as a product of the company, trade name HCA) or diphenylphosphine, and a phosphorus compound having an active hydrogen group directly bonded to a phosphorus atom and a phosphorus-containing phenol obtained by a reaction of an anthracene such as 4-benzoquinone or 1,4-naphthoquinone or the like, which is specifically, for example, 10-(2,5-dihydroxyphenyl)-10H-9-oxo-10-phosphine Phenanthrene-10-oxide (manufactured by Sanguang Co., Ltd., trade name HCA-HQ), 10-(1,4-dimethoxynaphthalene)-10H-9-oxo-10-phosphaphenanthrene-10-oxide Hereinafter referred to as HCA-NQ), diphenylphosphinyl hydroquinone (Beixing Chemical Industry) Manufactured by the company, trade name PPQ), diphenylphosphinyl-1,4-dimethoxynaphthalene, 1,4-cyclodecylphosphinyl-1,4-phenylene glycol (Japan Chemical Industry Co., Ltd. Manufactured by the company, trade name CPHO-HQ), 1,5-cyclo-octyl phosphinyl-1,4-phenyl diol (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ). However, the phosphorus compound (b) is not limited thereto, and these phosphorus compounds may be used in combination of two or more kinds.

Further, HCA-HQ containing a phosphorus-containing phenol compound can be used in JP-A-60-126293, HCA-NQ can be used in JP-A-61-236787, and PPQ can be used in zh. Obshch. Khim, 42 (11). The synthesis method shown in pages 2415-2418 (1972) is not limited thereto, and a known conventional method can be used.

Further, in order to enhance various characteristics, in addition to the phosphorus-containing compound, a compound (modifier) having a functional group reactive with an epoxy group can be reacted. For example, catechol, resorcinol, hydroquinones such as hydroquinone, diphenols, naphthols, trisphenols, bisphenol A, bisphenol F, bisphenol S, sinole BRG-555 (Phenol phenol novolak resin manufactured by Showa Denko Co., Ltd.), cresol novolac resin, alkyl phenol novolak resin, aralkyl phenol novolak resin, phenol novolak resin containing triazine ring, biphenyl aralkyl phenol resin a compound having two or more phenolic hydroxyl groups in one molecule such as a Regent TPM-100 (a trihydroxyphenylmethane novolak resin manufactured by Qunrong Chemical Industry Co., Ltd.) or an aralkyl naphthalenediol resin. Anthraquinone adipic acid, anthraquinone dioxime and the like, imidazole compounds and salts thereof, dicyandiamide, aminobenzoic acid esters, di-ethyltriamine, and three-folding Tetraamine, tetrazide An aromatic amine such as an aliphatic amine such as quinclomine, m-xylene diamine or isophorone diamine, diaminodiphenylmethane, diaminodiphenylanthracene or diaminoethylbenzene Anhydrides such as phthalic anhydride, trimellitic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl dianhydride, etc. These can be used in two or more types. The amount of the compound used is preferably 0.5 equivalent or less, preferably 0.2 equivalent or less, based on 1 equivalent of the epoxy group in the epoxy resin to be used. Further, when these compounds are used in combination with a compound containing phosphorus, the equivalent of the reactive group of the compounds is also included in the active hydrogen equivalent of the phosphorus compound of the formula (7), and the epoxy equivalent is preferably in the range of 50 to 95%.

The range in which the epoxy resin is 50 to 95% of the theoretical equivalent (T) means that the functional group of the reactive raw material may remain in the reaction between the epoxy resin (a) and the phosphorus compound (b). The residual function is based on the hardening reaction of the epoxy resin composition, and the hardener is reacted with the epoxy group to find an excellent hardened physical property.

Further, the epoxy resin containing phosphorus may be obtained by reacting 0.10 equivalent to 0.94 equivalent of the reactive functional group of the phosphorus compound (b) with respect to 1 equivalent of the epoxy group of the epoxy resin (a), preferably It is in the range of 0.20 equivalent to 0.70 equivalent, more preferably 0.20 equivalent to 0.60 equivalent. When the reactive functional group of the phosphorus compound (b) having 1 equivalent of the epoxy group of the epoxy group (a) is less than 0.10 equivalent, the flame retardancy is insufficient, and exceeding 0.94 equivalent increases the phosphorus-containing ring obtained by the reaction. Oxygen resin paint viscosity, which affects workability.

The epoxy equivalent of the phosphorus-containing epoxy resin is preferably in the range of 50% to 95% of the theoretical epoxy equivalent (T), preferably in the range of 70% to 95%, more preferably 75% to 90%. The scope. When it is less than 50%, a large amount of a flame-retardant phosphorus-containing phenol compound remains, and solvent solubility is lacking. When it is more than 95%, the viscosity when used as an epoxy resin paint is increased to affect workability. When it is in the range of 50% to 95% of the theoretical epoxy equivalent (T), the reactive functional group derived from the reactive raw material remains, and it acts as a hardener during the hardening reaction to contribute to the reaction.

The reaction temperature for the reaction for producing the epoxy resin containing phosphorus is preferably from 100 ° C to 250 ° C, more preferably from 130 ° C to 180 ° C. Below 100 ° C will significantly slow down the reaction, and above 250 ° C will be difficult to control the reaction of 50% ~ 95% of the theoretical epoxy equivalent.

Further, in the reaction for producing an epoxy resin containing phosphorus, a reaction catalyst may be used in order to promote the reaction if necessary. Catalysts which can be used, such as triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, etc., n-butyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide a quaternary ammonium salt such as a quaternary phosphonium salt such as a sulfonium salt, a 2-methyl-4-methylimidazole or a 2-phenylimidazole, a tetramethylammonium chloride or a tetraethylammonium bromide; A known conventional catalyst such as a tertiary amine such as triethylamine or benzyldimethylamine is not limited thereto. More preferred catalysts such as phosphines, particularly preferred catalysts are phosphines which are substituted by hydroxyl groups which may contain oxygen. The amount of the catalyst used is preferably in the range of 0.005% to 1% based on the reactive raw material.

The reaction of the epoxy resin with the reactive starting material can be carried out in a solvent-free or solvent-free manner, but when it is carried out in a solvent, it is preferably in an aprotic solvent. For example, toluene, xylene, methanol, ethanol, 2-butoxyethanol, dialkyl ether, glycol ether, propylene glycol monomethyl ether, dioxane, and the like are carried out. These reaction solvents may be used singly or in combination of two or more kinds. The amount of the reaction solvent used is preferably 50% or less of the total weight of the reactants.

Further, the reaction for producing the epoxy resin containing phosphorus can be carried out by adjusting the amount of the catalyst so that the epoxy equivalent is in the range of 50% to 95% of the theoretical epoxy equivalent, and the stepwise reaction can be carried out while adjusting the reaction temperature. The manufacturing method is known, but is not limited to these.

The epoxy resin composition according to the second embodiment of the present invention contains a phosphorus-containing epoxy resin as an essential component for an epoxy resin, and a multivalent resin of the general formula (12) used as a curing agent. The hydroxy resin and the filler are used as essential components, but may contain other epoxy resins, epoxy resin hardeners, hardening accelerators, fillers, and the like, if necessary.

That is, the epoxy resin used in the epoxy resin composition of the second embodiment of the present invention contains the above-mentioned phosphorus-containing epoxy resin as an essential component, but the phosphorus-containing epoxy resin does not impair physical properties. Other epoxy resins may be included in the range. The other epoxy resin is preferably a bifunctional or higher epoxy resin, for example, an epoxy resin used for synthesizing the above-mentioned phosphorus-containing epoxy resin, but is not limited thereto. Further, these epoxy resins may be used in combination of two or more kinds. In all of the epoxy resin components, the content of the phosphorus-containing epoxy resin may be 50% by weight or more, preferably 70% by weight or more.

Among them, the other epoxy resin is an epoxy resin represented by the general formula (19) having an epoxy equivalent of 200 g/eq or more, and the epoxy resin represented by the general formula (19) is used as an epoxy resin component. Again A range of 0% by weight or more and less than 50% by weight is preferred. A more desirable content range is from 5% by weight to 20% by weight of the epoxy resin component.

R _{9 in} the formula of the epoxy resin represented by the general formula (19) having an epoxy equivalent of 200 g/eq or more, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl In addition, the phenyl group, the methylphenyl group, the dimethylphenyl group, the α-methylbenzyl group, the α-pentyl group and the like may be used in combination of two or more kinds.

Further, when the epoxy resin represented by the general formula (19) is used, the hydroxypropyl group of the polar group formed during curing can be reduced, so that the dielectric constant and the dielectric loss tangent can be effectively reduced in addition to the flame retardancy and the moisture resistance. .

The amount of the hardener used in the epoxy resin composition of the second embodiment of the present invention is preferably from 0.5 to 1.3 equivalents, more preferably from 1 to 1.3 equivalents based on the theoretical epoxy equivalent of the epoxy resin. It is 0.7 to 1.1 equivalents. The content of the polyvalent hydroxy resin of the general formula (12) in the total hardener may be 15% by weight or more, preferably 25% by weight or more, and more preferably 50% by weight or more.

Further, when the fluidity or viscosity is adjusted, a diluent can be used insofar as the physical properties of the epoxy resin composition of the second embodiment of the present invention are not impaired. The diluent is preferably a reactive diluent, but may be a non-reactive diluent. a reactive diluent such as monofunctional glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether or the like, resorcinol glycidyl ether, neopentyl glycol glycidyl ether, 1, A polyfunctional glycidyl ether such as difunctional or glycerol polyglycidyl ether such as 6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether or pentaerythritol polyglycidyl ether. Non-reactive diluents such as benzyl alcohol, butyl diglycol, pine oil, and the like.

Further, in the epoxy resin composition of the second embodiment of the present invention, a curing accelerator may be used as necessary. For example, phosphines, quaternary guanidines, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3-(3,4-dichlorodiphenyl)-1,1 - dimethyl urea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, and the like. These hardening accelerators vary depending on the type of epoxy resin used, the type of epoxy resin hardener used, the molding method, the curing temperature, and the required characteristics, but the weight is preferably 0.01% to 20% relative to the weight of the epoxy resin. The range of % is more preferably 0.1% to 10%.

In the epoxy resin composition of the second embodiment of the present invention, other thermosetting resin or thermoplastic resin may be added in the range of non-destructive properties. For example, phenol resin, acrylic resin, petroleum resin, enamel resin, coumarone oxime resin, phenoxy ester resin, polyurethane, polyester, polyamine, polyimine, polyamidimide, Polyether phthalimide, polyphenylene ether, modified polyphenylene ether, polyether oxime, polyfluorene, polyetheretherketone, polyphenylene sulfide, polyvinyl formal, etc., but not limited In these.

The filler to be added to the epoxy resin composition of the second embodiment of the present invention is, for example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, boehmite, magnesium hydroxide, Talc, mica, calcium carbonate, calcium citrate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, cerium oxide alumina fiber, tantalum carbide fiber, Polyester fiber, cellulose fiber, aromatic polyamide fiber, and the like. The fillers are all relative to the epoxy resin composition The body is preferably from 1 to 70% by weight.

When the resin composition of the second embodiment of the epoxy is used as a plate-like substrate or the like, the filler is preferably a fibrous material from the viewpoints of dimensional stability and bending strength. More preferably, it is a glass fiber substrate obtained by weaving glass fibers in a mesh shape.

The epoxy resin composition of the second embodiment of the present invention may contain a decane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a shake imparting agent, a smoothing agent, a flame retardant, and a pigment, if necessary. Such as nuclear additives. These additives are preferably in the range of 0.01% to 20% by weight based on the epoxy resin composition.

The epoxy resin composition of the second embodiment of the present invention can be molded and hardened to obtain a cured product by the same method as the known epoxy resin composition. The molding method and the hardening method can be cured in the same manner as the known epoxy resin composition, for example, at 130 ° C to 200 ° C for 1 hour to 5 hours. Also, it can be used as a paint.

The cured epoxy resin according to the second embodiment of the present invention may be in the form of a laminate, a molded article, a laminate, a coating film, a film, or the like.

Example

The first embodiment and the second embodiment of the present invention are shown in the following examples and comparative examples, but the scope of the present invention is not limited to the examples. Unless otherwise stated, "parts" means parts by weight. Further, the analysis method and measurement method are as follows.

. Epoxy equivalent: according to JIS K7236.

. Phenolic hydroxyl equivalent: After adding THF containing 4% methanol to the sample, 10% tetrabutylammonium hydroxide was added, and the absorbance at a wavelength of 400 nm to 250 nm was measured using an ultraviolet visible spectrophotometer. The phenolic hydroxyl group used as the weight of the sample equivalent to 1 equivalent of the hydroxyl group was determined by using the calibration curve obtained by the same measurement method.

. Non-volatile ingredients: JIS K7235-1986

. Phosphorus content: After adding sulfuric acid, hydrochloric acid, or perchloric acid to the sample, it is heated and wet-ashed, and all phosphorus atoms are used as the orthophosphoric acid. After reacting metavanadate and molybdate in an acidic solution of sulfuric acid, the absorbance at 420 nm of the resulting phosphovanadate molybdate complex is measured, and the phosphorus atom content is determined by a previously prepared calibration curve. Expressed in % by weight. The phosphorus content of the laminate is expressed in terms of the content of the resin component relative to the laminate.

. Melt viscosity: measured at 150 ° C using a conical plate viscometer (ASP-MG manufactured by East Asia Industries Co., Ltd.).

. Glass tempering temperature: DMS6100 manufactured by SII Nano Technology Co., Ltd., measured by IPC-TM-650 2.4.24.2.

. Dielectric coefficient, dielectric loss tangent: Using a dielectric analyzer/AGILENT Technologies, the volumetric method was used to evaluate the dielectric constant of 1 GHz and the dielectric loss tangent.

. Flammability: According to UL94 (Safety Certification Specification of Underwriters Laboratories Inc.). After the test of the five test pieces, the total time of the burning duration after the first and second firings (5 times for each of the five times) was expressed in seconds.

. Interlaminar peel strength (interlayer adhesion): according to JIS C6481.

[related to the first embodiment] Synthesis Example 1

105 g of a phenol novolak (BRG-555, a hydroxyl group equivalent of 105 g/eq., a softening point of 67 ° C, and a melt viscosity of 0.018 Pa.s at 150 ° C) was placed in a 1 L four-necked flask and heated to 140 °C. Next, 0.099 g of p-toluenesulfonic acid (500 ppm relative to the phenol novolac and styrene) was introduced as an acid catalyst while stirring at 140 ° C, and 93.6 g of styrene (0.9 mol) was added dropwise over 3 hours. ) carry out the reaction. After reacting at 140 ° C for 2 hours, 0.163 g of 30% Na ₂ CO _{3 was added} for neutralization. Next, it was dissolved in 330 g of MIBK, and washed with water 5 times at 80 °C. Next, MIBK was distilled off under reduced pressure, and 198 g of a polyvalent hydroxy resin. Its hydroxyl equivalent is 199g / eq., the softening point is 77 ° C, the melt viscosity at 150 ° C is 0.23Pa. s, the general formula (3) has an average of 3.3 and a p of 0.9. This resin is called StPN-A.

Synthesis Example 2

105 g of a phenol novolak (BRG-555) was placed in a 1 L four-necked flask and heated to 140 °C. Next, while stirring at 140 ° C, 0.115 g of p-toluenesulfonic acid (500 ppm of phenol novolac and styrene) was introduced as an acid catalyst, and 135.2 g (1.3 mol) of styrene was added dropwise over 3 hours. reaction. After reacting at 140 ° C for 2 hours, 0.187 g of 30% Na ₂ CO _{3 was added} for neutralization. Next, it was dissolved in 330 g of MIBK, and washed with water 5 times at 80 °C. Then, MIBK was distilled off under reduced pressure, and 229 g of a polyvalent hydroxy resin. Its hydroxyl equivalent is 235g / eq., the softening point is 78 ° C, the melt viscosity at 150 ° C is 0.26Pa. s, n averages 3.3 and p is 1.3. This resin is called StPN-B.

Synthesis Example 3

514 parts of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (manufactured by Sanguang Co., Ltd., trade name HCA, phosphorus content 14.2% by weight) and 1,4-naphthoquinone 79 parts, 490 parts of toluene was placed in a four-piece glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction tube, and stirred at 75 ° C for 30 minutes, and then the reaction was carried out at 110 ° C for 90 minutes while removing the moisture in the system. Further, toluene was removed to obtain 10-(1,4-dioxophthalene)-10H-9-oxo-10-phosphaphenanthrene-10-oxide (HCA-NQ). 1240 parts of a phenol novolac type epoxy resin (trade name: YDPN-638, epoxy equivalent: 175 g/eq.), and 0.51 part of triphenylphosphine (TPP) as a catalyst were added. The reaction was carried out at ° C for 4.5 hours and then diluted with MEK. The obtained epoxy resin containing phosphorus is dark brown transparent, non-volatile content 70%, solution viscosity 1900 mPa. s, epoxy equivalent 392 g / eq., phosphorus content 3.5%. The theoretical epoxy equivalent is 382 g/eq., and the ratio of the measured epoxy equivalent to the theoretical epoxy equivalent is 103%. This resin is referred to as epoxy resin A.

Synthesis Example 4

432 parts of HCA, 79 parts of 1,4-naphthoquinone, and 490 parts of toluene were placed in four-piece glass equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction tube. After stirring at 75 ° C for 30 minutes in a separable flask, the reaction was carried out at 110 ° C for 90 minutes while removing the moisture in the system, and then toluene was removed to obtain HCA-NQ. After adding 1240 parts of YDPN-638 and 0.15 parts of TPP, the reaction was carried out at 165 ° C for 4.5 hours, and then diluted with MEK. The obtained epoxy resin solution containing phosphorus is dark brown transparent, non-volatile component 70%, paint viscosity 300mPa. s, the measured epoxy equivalent was 292 g/eq., the hydroxyl equivalent was 3600 g/eq., and the phosphorus content was 3.5%. Further, the functional group of the compound (b) having a reactive functional group of 1 equivalent with respect to the epoxy group of the epoxy resin (a) is 0.30 equivalent, and the theoretical epoxy equivalent is 382 g/eq., relative to the theoretical ring. The ratio of the measured epoxy equivalent of the oxygen equivalent was 76%. This resin is referred to as epoxy resin B.

Synthesis Example 5

150 g of StPN-A obtained in Synthesis Example 1, 419 g of epichlorohydrin, and 63 g of diethylene glycol dimethyl ether were placed in a four-neckable flask and stirred to dissolve. After uniformly dissolving, while maintaining a temperature of 65 ° C under a reduced pressure of 130 mmHg, 62.9 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water and the epichlorohydrin were separated by separation in a separation tank. The chloropropane is returned to the reaction vessel, and the water is removed to the outside of the system for reaction. After completion of the reaction, the salt formed was removed by filtration, washed with water, and then epichlorohydrin was distilled off to obtain 180 g of an epoxy resin. The obtained resin has an epoxy equivalent of 270 g/eq., a softening point of 61 ° C, and a melt viscosity of 0.13 Pa at 150 ° C. s. This epoxy resin is called StPNE.

Examples 1 to 6, Comparative Examples 1 to 4

The polyvalent hydroxy resin (StPN-A, StPN-B) obtained by the above synthesis, epoxy resin A, epoxy resin B, epoxy resin StPNE, and 2-ethyl-4-methylimidazole used as a hardening accelerator (2E4MZ) was dissolved in a solvent (methyl ethyl ketone, methoxypropanol) to give a nonvolatile content of 50%. The epoxy resin paint was prepared according to the addition ratio indicated in Tables 1 and 2. The numerical values in the table indicate the parts by weight when added. PN is the hardener component of BRG-555. FX-289B is a phosphorus-containing epoxy resin manufactured by Nippon Steel Chemical Co., Ltd. The phosphorus content is the P content in the resin composition. DICY is a dicyandiamide hardener.

As shown in Examples 1 to 6, the cured product of the epoxy resin composition of the present invention was judged to have excellent dielectric properties and flame retardancy. Even if the prior art used an amine-based curing agent as in Comparative Example 1, and the phosphorus content of the composition was increased as shown in Comparative Example 3, the flame retardancy was imparted, but the dielectric properties were deteriorated. Further, the epoxy resin composition of the present invention can obtain a cured product having excellent adhesion at the same time.

[Regarding the second embodiment] Epoxy resin used

. Yeppes FX-305EK70 (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 493g/eq, phosphorus content 3.0%)

. Yeppes FX-289BEK75 (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 305g/eq, phosphorus content 2.0%)

Hardener used

. Xiu Nuoer BRG-555 (made by Showa Denko Co., Ltd., phenolic hydroxyl equivalent of 105g / eq.)

. Dicyanamide (hereinafter referred to as DICY) (manufactured by Kabate, Japan, active hydroxyl equivalent 21 g/eq)

Synthesis Example 6

162 parts of o-cresol, 90 parts of formaldehyde, and 100 parts of water were placed in a synthesis apparatus equipped with a thermometer, a cooling tube, a dropping funnel, an inert gas introduction port, and a stirrer, and nitrogen was introduced while stirring. At room temperature, while paying attention to heat, 50 parts of a 15% aqueous sodium hydroxide solution was slowly added dropwise. Thereafter, the reaction was carried out at 50 ° C for 10 hours. After the completion of the reaction, 300 parts of water was added thereto, which was cooled to room temperature, and then neutralized with a 10% aqueous hydrochloric acid solution. After the precipitated crystals were filtered off, the filtrate was washed to pH 6 to 7. Drying at 50 ° C under reduced pressure gave 197 parts of white crystals. 260 parts of ?-naphthol and 1200 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) were added to 197 parts of the obtained white crystals, and stirred at room temperature under a nitrogen atmosphere. Next, pay attention to the heat while slowly adding 2 parts of p-toluenesulfonic acid. The reaction was carried out for 2 hours after heating to 50 °C. After neutralizing with a 15% aqueous sodium hydroxide solution, it was washed with water until neutral. The MIBK was recovered under reduced pressure to obtain a polyvalent hydroxy resin of the general formula (12). The obtained polyvalent hydroxy resin had a softening point of 132 ° C and a phenolic hydroxyl equivalent of 147 g / eq.

Synthesis Example 7

105 g of phenol novolak (made by Showa Polymer; BRG-555, hydroxyl equivalent 105 g/eq., softening point 67 ° C, melt viscosity at 150 ° C, 0.08 Pa.s) was placed in the same apparatus as in Synthesis Example 6 to raise the temperature to 140 ° C. Next, 0.099 g (500 ppm) of p-toluenesulfonic acid used as an acid catalyst was introduced while stirring at 140 ° C, and 93.6 g (0.9 mol) of styrene was added dropwise thereto over 3 hours to carry out a reaction. Further, after reacting at 140 ° C for 2 hours, 0.163 g of 30% Na ₂ CO _{3 was} added for neutralization. The solution was dissolved in 330 g of MIBK and washed 5 times at 80 ° C. Then, MIBK was distilled off under reduced pressure to obtain 198 g of a polyvalent hydroxy resin of a styrenated phenol novolak resin. Its hydroxyl equivalent is 199g / eq., the softening point is 77 ° C, the melt viscosity at 150 ° C is 0.23Pa. s, n averages 3.3 and p is 0.9.

Synthesis Example 8

150 g of the polyvalent hydroxy resin obtained in Synthesis Example 7, 419 g of epichlorohydrin, and 63 g of diethylene glycol dimethyl ether were placed in the same apparatus as in Synthesis Example 6, and stirred and dissolved. After uniformly dissolving, while maintaining a temperature of 65 ° C under a reduced pressure of 130 mmHg, 62.9 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the distilled water and the epichlorohydrin were separated in a separating tank to remove the epoxy chlorine. Propane is returned to the reaction vessel, and the water is removed to the outside of the system for reaction. After completion of the reaction, the resulting salt was filtered off, washed with water, and then epichlorohydrin was distilled off to obtain 180 g of an epoxy resin represented by the general formula (19). The obtained styrenated phenol novolac type epoxy resin has an epoxy equivalent of 270 g/eq., a softening point of 61 ° C, and a melt viscosity of 0.13 Pa at 150 ° C. s.

Synthesis Example 9

9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA, phosphorus content 14.2% by weight) 432 parts and 1,4-naphthoquinone (Kawasaki Chemicals) 79 parts of Industrial Co., Ltd. and 920 parts of toluene were placed in the same apparatus as in Synthesis Example 6, and stirred at 75 ° C for 30 minutes, and then the water in the system was removed while reacting at 110 ° C for 90 minutes, and then toluene was removed to obtain 10- (1,4-Dimethoxynaphthalene)-10H-9-oxo-10-phosphaphenanthrene-10-oxide (HCA-NQ). 1240 parts of a phenol novolac type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name: YDPN-638, epoxy equivalent: 175 g/eq.) was added as a catalyst for triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) After 0.51 parts of TPP), the reaction was carried out at 165 ° C for 4.5 hours, and then diluted with methyl ethyl ketone. The obtained epoxy resin solution containing phosphorus is dark brown transparent, non-volatile component 70%, solution viscosity 1900 mPa. s, epoxy equivalent 392 g / eq., phosphorus content 3.5%. Further, with respect to 1 equivalent of the epoxy group of the YDPN-638 of the epoxy resin for synthesis (a), the function of the reactant of the compound (b) having a reactive functional group (H) and 1,4-naphthoquinone The base is 0.35 equivalents. The theoretical epoxy equivalent (T) was 382 g/eq., and the ratio of the measured epoxy equivalent to the theoretical epoxy equivalent was 103%.

Synthesis Example 10

The same operation as in Synthesis Example 9 was carried out except that 0.10 part of TPP as a catalyst was added. The obtained epoxy resin solution containing phosphorus is dark brown transparent, non-volatile component 70%, paint viscosity 300mPa. s, measured epoxy equivalent 292 g / eq., hydroxyl equivalent 3600 g / eq., phosphorus content 3.5%. Further, it is equivalent to 1 equivalent of the epoxy group of YDPN-638 of the epoxy resin (a). The functional group of the reactant of HCA and 1,4-naphthoquinone of the compound (b) having a reactive functional group is 0.35 equivalent. The theoretical epoxy equivalent (T) was 382 g/eq., and the ratio of the measured epoxy equivalent to the theoretical epoxy equivalent was 76%.

Synthesis Example 11

The same operation as in Synthesis Example 9 was carried out except that 401 parts of HCA, 73 parts of 1,4-naphthoquinone, 958.2 parts of YDPN-638, and 0.14 parts of a catalyst were used. The obtained epoxy resin solution containing phosphorus is dark brown transparent, non-volatile content 70%, paint viscosity 6730 mPa. s, measured epoxy equivalent 428 g / eq., hydroxyl equivalent 5049 g / eq., phosphorus content 4.0%. Further, the functional group of the reactant of HCA and 1,4-naphthoquinone of the compound (b) having a reactive functional group is 0.42 with respect to 1 equivalent of the epoxy group of YDPN-638 of the epoxy resin (a). equivalent. The theoretical epoxy equivalent (T) was 468 g/eq., and the ratio of the measured epoxy equivalent to the theoretical epoxy equivalent was 94%.

Synthesis Example 12

In addition to 211 parts of HCA and 152 parts of 1,4-naphthoquinone, YDF-170 (epoxide equivalent of bisphenol F type epoxy resin, epoxide equivalent 170g/eq.) was replaced by 637 parts of YDPN-638. The same operation as in Synthesis Example 9 was carried out except that the catalyst was 0.07 parts. The obtained epoxy resin solution containing phosphorus is dark brown transparent, non-volatile component 80%, paint viscosity 2950 mPa. s, measured epoxy equivalent 403 g / eq., hydroxyl equivalent 1506 g / eq., phosphorus content 3.0%. Further, the epoxy group of YDF-170 relative to the epoxy resin (a) The functional group of the reactant of HCA and 1,4-naphthoquinone of 1 equivalent of the compound having a reactive functional group (b) was 0.53 equivalent. The theoretical epoxy equivalent (T) was 551 g/eq., and the ratio of the measured epoxy equivalent to the theoretical epoxy equivalent was 73%.

Synthesis Example 13

The same operation as in Synthesis Example 12 was carried out except that HCA was 204 parts, 1,4-naphthoquinone was 145 parts, YDF-170 was 375 parts, and the catalyst was 0.28 parts. The obtained epoxy resin solution containing phosphorus is dark brown transparent, non-volatile component 80%, paint viscosity 2930 mPa. s, measured epoxy equivalent 1114g / eq., hydroxyl equivalent 2725g / eq., phosphorus content 4.0%. Further, the functional group of the reactant of HCA and 1,4-naphthoquinone of the compound (b) having a reactive functional group is 0.84 based on 1 equivalent of the epoxy group of YDF-170 of the epoxy resin (a). equivalent. The theoretical epoxy equivalent (T) was 1885 g/eq., and the ratio of the measured epoxy equivalent to the theoretical epoxy equivalent was 59%.

Examples 7 to 12 and Comparative Examples 6 to 13

The polyvalent hydroxy resin obtained in the above Synthesis Examples 6 to 13 and epoxy resin, FX-305, FX-289B, BRG-555, and 2-ethyl-4-methylimidazole as a curing accelerator (hereinafter It is called 2E4MZ) dissolved in a solvent, and the epoxy resin varnish is added in a ratio as shown in Table 3. The numerical values in the table indicate the parts by weight when added. The epoxy resin varnish obtained by impregnating a glass fiber cloth (WEA 116E106S136, manufactured by Nitto Denko Co., Ltd., thickness: 0.1 mm) was dried in a hot air circulating oven at 150 ° C for 11 minutes to obtain a prepreg. . 6 pieces of prepreg obtained by superposition and copper foil (3EC-III, manufactured by Mitsui Metals and Minerals Co., Ltd., thickness 35 μm) were vacuum-pressed at a temperature of 130 ° C × 15 minutes + 190 ° C × 80 minutes to obtain a pressure of 2 MPa. 0.8mm thick laminate. The evaluation results of the laminates are shown in Table 3.

In the examples 7 to 12, the epoxy resin composition of the present invention has a dielectric property superior to that of Comparative Example 6 in which a phosphorus-containing epoxy resin and a DICY composition are present, and a comparative example is obtained. 7 to Comparative Example 13 The epoxy resin composition maintains dielectric properties while having excellent flame retardancy and adhesion. For example, the balance of dielectric properties, flame retardancy, adhesion, and heat resistance can be obtained only by combining a specific phosphorus-containing epoxy resin, a specific polyvalent hydroxy resin, and a filler.

Claims (11)

An epoxy resin composition characterized by containing an epoxy resin and a hardener, or an epoxy resin composition of the filler and the filler, containing a phosphorus content of 1.0 to 6.0% by weight as an epoxy resin component Phosphorus epoxy resin, and a polyvalent hydroxy resin represented by the following general formula (1) used as a hardener component, (wherein A represents a benzene ring or a naphthalene ring, Z represents CH ₂ or a structure represented by the following general formula (2), R represents hydrogen, or a hydrocarbon group having 1 to 14 carbon atoms which may contain oxygen, and R' represents hydrogen Or a hydrocarbon group having 1 to 6 carbon atoms, n represents the number from 0 to 20, p represents the number from 0.1 to 6, but the total carbon number of A+R is 9 or more, and when all A is a naphthalene ring, at least one Z is generally Formula (2)) (wherein R and p are synonymous with the general formula (1)). The epoxy resin composition of claim 1, wherein the hardener component is a polyvalent hydroxy resin represented by the following general formula (3), (wherein R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents a substituent represented by the following general formula (4), n represents a number of 1 to 20, and p represents a number of 0.1 to 2.5) (wherein R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). The epoxy resin composition of claim 2, wherein the epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and containing the general formula (5) and/or a phosphorus-containing epoxy resin obtained by reacting an epoxy group of the phosphorus compound (b) represented by the formula (7) with a reactive material, (wherein X is hydrogen or a group represented by formula (6), q represents 0 or 1, and R ₄ and R ₅ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₄ and R ₅ may be bonded and phosphorus Atom and oxygen atoms together form a ring) (Y represents a aryl group with a carbon number of 6 to 20) (wherein X is hydrogen or a group represented by formula (6), r represents 0 or 1, and R ₆ and R ₇ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₆ and R ₇ may be bonded and phosphorus The atoms and oxygen atoms together form a ring). An epoxy resin composition according to claim 2 or 3, wherein the epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and the general formula (5) and/or Or a phosphorus-containing epoxy resin obtained by reacting the phosphorus compound (b) represented by the general formula (7), and the epoxy equivalent of the phosphorus-containing epoxy resin is a theoretical epoxy obtained by the following formula (8) The range of 50 to 95% of the equivalent (T), T = [(a1) + (b1)] / (AB) (8) where (a1) is the amount (g) of the epoxy resin (a), ( B1) is the amount (g) of the phosphorus compound (b), A is the value obtained by the formula (9), and B is the value obtained by the formula (10) A = (a1) / epoxy of the epoxy resin Equivalent (9) B = (b1) / active hydrogen equivalent of the phosphorus compound (10). The epoxy resin composition of claim 2 or 3, wherein the epoxy resin component further contains 5 to 50% by weight of the epoxy resin represented by the general formula (11). (wherein G represents a glycidyl group, and R ₁ , R ₂ , n and p are synonymous with the general formula (3)). The epoxy resin composition of claim 1, wherein the hardener component is a polyvalent hydroxy resin represented by the following general formula (12), (wherein R ₈ represents hydrogen or a hydrocarbon group having 1 to 9 carbon atoms which may contain oxygen, n represents a number of 0 to 20, and p represents a number of 3 to 6). The epoxy resin composition of claim 6, wherein the epoxy resin containing phosphorus is an epoxy resin (a) having two or more epoxy groups in one molecule, and the general formula (13) and/or a phosphorus-containing epoxy resin obtained by reacting the phosphorus compound (b) represented by the formula (15), (wherein X is hydrogen or a group represented by formula (14), q represents 0 or 1, and R ₄ and R ₅ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₄ and R ₅ may be bonded and phosphorus Atom and oxygen atoms together form a ring) (Y represents a aryl group with a carbon number of 6 to 20) (wherein X is hydrogen or a group represented by formula (14), r represents 0 or 1, and R ₆ and R ₇ independently represent a hydrocarbon group having 1 to 6 carbon atoms, but R ₆ and R ₇ may be bonded and phosphorus The atoms and oxygen atoms together form a ring). The epoxy resin composition of claim 6 or 7, wherein the epoxy equivalent of the epoxy resin containing phosphorus is in the range of 50 to 95% of the theoretical epoxy equivalent (T) obtained by the following formula (16). T=[(a1)+(b1)]/(AB) (16) where (a1) is the weight (g) of the epoxy resin (a), and (b1) is the weight of the phosphorus compound (b) ( g), A is a value obtained by the following formula (17), and B is a value obtained by the following formula (18): A = (a1) / epoxy equivalent of the epoxy resin (17) B = (b1) / The active hydrogen equivalent of the phosphorus compound (18). The epoxy resin composition according to claim 6 or 7, wherein the epoxy resin is 5% to 50% by weight based on the total amount of the epoxy resin, and the epoxy equivalent of 200 g/eq or more is the following general formula (19). Represented epoxy resin, (wherein G represents a glycidyl group, R ₉ represents hydrogen or a hydrocarbon group having 1 to 9 carbon atoms, and m represents a number of 1 to 20). The epoxy resin composition of claim 1, wherein the filler is a fibrous glass substrate. An epoxy resin cured product which is formed by hardening an epoxy resin composition as claimed in claim 1.