TW201529698A - Phosphorus-containing epoxy resin composition and cured article - Google Patents

Abstract

Provided is a phosphorus-containing epoxy resin composition having adequate flame retardancy which is obtained by increasing the phosphorous content, while having a low viscosity and excellent solubility in organic solvents. This phosphorous-containing epoxy resin composition does not precipitate at room temperature, and is obtained by dissolving 5-45 parts by mass of a phosphorous-containing phenol compound represented by general formula (2) in 100 parts by mass of a phosphorous-containing epoxy resin represented by the general formula (1) and having a phosphoric content that falls within the range of 2-7 mass%. [Compound represented by formula 1] (in the formula, R1 and R2 represent C1-6 hydrocarbon groups, which may be the same or different , and may form a ring together with phosphorus atoms. i represents 0 or 1. [Compound represented by formula 2] (in the formula, R3 and R4 represent C1-6 hydrocarbon groups, which may be the same or different, and may form a ring together with phosphorus atoms. n represents 0 or 1. A represents a C6-20 arene-triyl group).

Description

Phosphorus-containing epoxy resin composition and hardened material

The present invention relates to a phosphorus-containing epoxy resin composition comprising a phosphorus-containing epoxy resin and a phosphorus-containing phenol compound and a hardened material thereof.

Since epoxy resin is excellent in adhesiveness, heat resistance, and moldability, it is widely used in industrial applications including the electric-electronics field. In particular, in the case of a laminate used in the electrical-electronic field, flame retardancy is strongly required in terms of safety such as the purpose of preventing fire during use of the machine. In the past, as a method of imparting flame retardancy to a laminate, a bromine-based flame retardant, a nitrogen-based flame retardant, and a phosphorus-based flame retardant are used alone or in combination, and the flame retardant is used in a large amount. A system using inorganic flame retardant additives. However, regarding the environmental problems in recent years, when a halogen compound is used, it is suspected that a harmful halide is formed during the combustion treatment of the laminate, and the demand for a so-called halogen-free flame-retardant system that does not use a bromine-based flame retardant becomes strong. . Therefore, in the prior art, in order to impart flame retardancy to the laminated board without using a bromine-based flame retardant, it is necessary to use a nitrogen-based flame retardant or a phosphorus-based flame retardant, but the nitrogen-based flame retardant imparts flame retardancy. In addition, among the phosphorus-based flame retardants, the safety of red phosphorus is insufficient, and the phosphate-based compound is liquid, so that bleeding is likely to occur, and in the case of using phosphates, heat resistance or adhesion of the solder is lowered, which is difficult. Used as a laminate.

For the above problems, it is disclosed in Patent Documents 1 and 2 that 10-(2,5-dihydroxybenzene is used. Base) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ manufactured by Sanko Co., Ltd.) and thermosetting of epoxy resin obtained by specific molar ratio reaction Resin and composition. Further, Patent Document 3 discloses a phosphorus-containing epoxy resin obtained by reacting a resin having a difunctional or higher epoxy group with diphenylphosphinyl hydroquinone. However, the phosphorus-containing epoxy resin obtained by the reaction of the phosphorus compound with the epoxy resin has a higher molecular weight as the phosphorus content becomes higher, so that the viscosity of the resin varnish having sufficient flame retardancy is higher. The workability during the operation or the impregnation of the substrate such as the glass cloth is deteriorated. Further, since the crosslinking density of the cured product is lowered due to the increase in the molecular weight of the phosphorus-containing epoxy resin, it is difficult to obtain a high glass transition temperature.

In this regard, Patent Document 4 discloses that a compound derived from phosphorus-containing phenol is formed by making A method for reducing the molecular weight and reducing the viscosity of a phosphorus-containing epoxy resin having a hydroxyl group. However, in this method, it is necessary to react the phosphorus-containing phenol compound with the epoxy resin to some extent, so that the viscosity is lowered from the viewpoint of the decrease in viscosity.

Further, Patent Document 5 discloses that it is impossible to obtain only a phosphorus-containing epoxy resin. It is fully flame retardant, so the phosphorus compound is dissolved in the phosphorus-containing epoxy resin varnish to increase the phosphorus content. However, the solvent must use a high boiling point solvent such as N,N-dimethylformamide or a phosphorus compound. Problems that are easy to precipitate. Patent Document 6 discloses a method in which HCA-HQ is dispersed in a resin varnish by finely pulverizing into an average particle diameter of 10 μm and a maximum particle diameter of 40 μm, but the viscosity is more than that in the case of using a high-boiling solvent to dissolve the phosphorus compound. It is easy to become high, and in order to sufficiently carry out the hardening reaction, it is necessary to sufficiently check the problem of the hardening conditions.

[Patent Document 1] Japanese Patent - 3092009

[Patent Document 2] Japanese Patent Laid-Open No. 11-279258

[Patent Document 3] Japanese Patent Laid-Open No. 5-214070

[Patent Document 4] Japanese Special Open 2012-172079

[Patent Document 5] Japanese Special Opening 2002-249540

[Patent Document 6] Japanese Special Publication 2003-011269

[Patent Document 7] Japanese Patent Laid-Open No. 60-126293

[Patent Document 8] Japanese Patent Laid-Open No. 61-236787

[Non-Patent Document 1] zh. Obshch. Khim, 42 (11), pp. 2415-2418 (1972)

When the phosphorus-containing epoxy resin or the phosphorus-containing epoxy resin composition used so far is used to increase the phosphorus content in order to improve the flame retardancy, the solubility in a solvent is deteriorated, and further, the viscosity is high, which makes it difficult to increase the viscosity. Applied to laminates. Further, when the phosphorus-containing phenol compound lacks solubility in an organic solvent and is used as a blend for substrate use, it is difficult to apply it as a uniform resin varnish. The present invention has been made in view of the above problems in the prior art, and has a sufficient flame retardancy by increasing the phosphorus content, and has low viscosity and good solubility in an organic solvent, and is suitable for a fibrous substrate. An epoxy resin composition which is excellent in workability such as impregnation.

That is, the present invention is: (1) A phosphorus-containing epoxy resin composition containing phosphorus-containing epoxy in a range of 2 to 7 mass% with respect to a phosphorus having a structure of the following formula (1) 100 parts by mass of the resin, and 5 to 45 parts by mass of the phosphorus-containing phenol compound represented by the following formula (2) is dissolved, and no precipitation occurs at room temperature.

(wherein R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a cyclic ring together with a phosphorus atom; i represents 0 or 1)

(wherein R ₃ and R ₄ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may be cyclic together with a phosphorus atom; n represents 0 or 1; and A represents an aromatic hydrocarbon having 6 to 20 carbon atoms; Three base (arenetriyl);

(2) The phosphorus-containing epoxy resin composition according to (1), which is obtained by blending an epoxy resin (B);

(3) The phosphorus-containing epoxy resin composition according to (2), characterized in that the phosphorus content is 2% by mass or more;

(4) The phosphorus-containing epoxy resin composition according to any one of (1) to (3), which is obtained by blending a curing agent (C);

(5) A prepreg obtained by impregnating a fibrous base material with the phosphorus-containing epoxy resin composition according to any one of (1) to (4);

(6) A cured product obtained by hardening the phosphorus-containing epoxy resin composition according to any one of (1) to (4);

(7) A cured product obtained by curing the prepreg according to (5).

Regarding the phosphorus-containing epoxy resin composition of the present invention, it was found that it was previously difficult to dissolve The phosphorus phenol compound can be dissolved in a specific phosphorus-containing epoxy resin, thereby completing the present invention, and has both the flame retardancy obtained from a high phosphorus content and the workability obtained from a low resin viscosity. The phosphorus-containing epoxy resin composition of the present invention is easy to impregnate a fibrous substrate such as glass cloth in the production of a laminate, and is improved in flame retardancy, so that it can be used for printed wiring substrate materials in the electronic and electrical fields. , sealing materials, casting materials, adhesive materials, and aerospace or composite materials used in vehicles, bridges, windmills, etc., which require flame retardancy.

Hereinafter, embodiments of the present invention will be described in detail.

The phosphorus-containing epoxy resin used in the present invention has a chemical structure represented by the following formula (1) in its molecule, and for example, the following formula (2) and/or the following formula ( 3) The phosphorus compound represented by the reaction is synthesized by reacting with an epoxy resin.

(wherein R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a cyclic ring together with a phosphorus atom; i represents 0 or 1)

(wherein R ₃ and R ₄ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may be cyclic together with a phosphorus atom; n represents 0 or 1; and A represents an aromatic hydrocarbon having 6 to 20 carbon atoms; Three bases)

(wherein R ₅ and R ₆ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom; j represents 0 or 1)

Examples of the phosphorus compound represented by the above formula (2) or the above formula (3) include 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene- 10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ), 10-(1,4-dihydroxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA-NQ), diphenylphosphinyl hydroquinone (manufactured by Behind Chemical Industry Co., Ltd., trade name PPQ), diphenylphenylphosphino-1,4-dihydroxynaphthalene, 1,4-stretch Cyclooctylphosphinyl-1,4-benzenediol (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ), 1,5-cyclooctylphosphinyl-1,4-benzenediol ( Phosphorus-containing phenols, manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., A trade name HCA), a mixture of 1,4-cyclooctylphosphine oxide and 1,5-cyclooctylphosphine oxide (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO), diphenylphosphine oxide, etc., but Not limited to these.

Further, the epoxy resin which reacts with the above phosphorus compound in the synthesis of the phosphorus-containing epoxy resin has at least 1.5 epoxy groups in the molecule, more preferably two or more. In the case where the phosphorus compound of the formula (3) is used in combination, it is preferred to use a group having three or more epoxy groups. Examples of the epoxy resin include Epotohto YD-128, Epotohto YD-8125 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol A type epoxy resin), Epotohto YDF-170, and Epotohto YDF-8170 (new Manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol F-type epoxy resin), YSLV-80XY (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., tetramethyl bisphenol F-type epoxy resin), Epotohto YDC-1312 (new Manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroquinone epoxy resin), jER YX-4000H (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), Epotohto YDPN-638, Epotohto YDPN-63X (new Manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., phenol novolak type epoxy resin), Epotohto YDCN-701 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., cresol novolak type epoxy resin), Epotohto ZX-1201 (New Day) Manufactured by Tiejinjin Chemical Co., Ltd., bisphenol oxime epoxy resin), TX-0710 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol S-type epoxy resin), Epiclon EXA-1515 (Japan Chemical Industry Co., Ltd.) Co., Ltd. manufacture, bisphenol S Epoxy resin), NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl phenol epoxy resin), Epotohto ZX-1355, Epotohto ZX-1711 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., naphthalene Diphenol type epoxy resin), Epotohto ESN-155 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., β-naphthol aralkyl type epoxy resin), Epotohto ESN-355, Epotohto ESN-375 (Nippon Steel & Living Gold Manufactured by Chemical Co., Ltd., dinaphthol aralkyl type epoxy resin), Epotohto ESN475V, Epotohto ESN-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., α-naphthol aralkyl type epoxy resin), EPPN -501H (manufactured by Nippon Kayaku Co., Ltd., triphenylmethane type epoxy resin), Sumiepoxy TMH-574 (manufactured by Sumitomo Chemical Co., Ltd., triphenylmethane type epoxy resin), YSLV-120TE (Nippon Steel Sumitomo Chemical Co., Ltd., Disulfide Epoxy Resin), Epotohto ZX-1684 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., resorcinol type epoxy resin), Denacol EX-201 (Nagase ChemteX Limited) Made by the company, resorcinol type epoxy tree Epiclon HP-7200H (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), epoxy resin made of phenolic compound of polyphenol resin and epihalohydrin, TX-0929, TX-0934, TX-1032 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., alkylene glycol type epoxy resin), etc., epoxy resin manufactured by alcohol compound and epihalohydrin, Celloxide 2021 (manufactured by Daicel Chemical Industry Co., Ltd.) , an aliphatic cyclic epoxy resin), Epotohto YH-434 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., diaminodiphenylmethane tetraglycidylamine), and the like, which is made of an amine compound and an epihalohydrin. Resin, jER 630 (manufactured by Mitsubishi Chemical Corporation, Aminophenol-based epoxy resin), Epotohto FX-289B, Epotohto FX-305, TX-0932A (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., phosphorus-containing epoxy resin) a phosphorus-containing epoxy resin, an urethane modified epoxy resin obtained by reacting an epoxy resin with a modifying agent such as a phosphorus compound, or the like The epoxy resin of the oxazolidinone ring, etc. is not limited to these. Further, these epoxy resins may be used singly or in combination of two or more.

Phosphorus compound and epoxy resin of the above formula (2) and/or the above formula (3) The reaction can be carried out by a publicly known method such as the Advance method which is a reaction method of a phenol compound and an epoxy resin, including the methods described in Patent Documents 1, 2, and 3. At this time, regarding the ratio of the phosphorus compound to the epoxy resin, the phosphorus content of the phosphorus-containing epoxy resin obtained after the reaction must be in the range of 2 to 7 mass%, more preferably 2.5 to 5 mass%. If the phosphorus content is small, the solubility of the phosphorus-containing phenol compound used in the present invention and the phosphorus-containing epoxy resin is deteriorated. If the phosphorus content is high, the viscosity of the phosphorus-containing epoxy resin is changed. High, dissolving phosphorus-containing phenolic compounds has also become difficult.

Moreover, in the reaction between the phosphorus compound and the epoxy resin, it may be necessary to promote the reaction The reaction catalyst should be used instead. Examples of the catalyst that can be used include phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine, n-butyltriphenylphosphonium bromide, and ethyltriphenyl. Tertiary sulfonium salts such as cesium iodide, imidazoles such as 2-ethyl-4-methylimidazole and 2-benzimidazole, tetra-ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, and triethyl ethoxide A known conventional catalyst such as a tertiary amine such as an amine or dimethylbenzylamine is not limited thereto. The amount of use of the catalyst is preferably in the range of 0.002 to 2 parts by mass based on 100 parts by total of the epoxy resin and the phosphorus compound. If the amount is increased, there is a problem that the stability of the phosphorus-containing epoxy resin composition of the present invention is adversely affected.

As the phosphorus-containing phenol compound dissolved in the phosphorus-containing epoxy resin, The structure shown by the formula (2). Specific examples thereof include phosphorus-containing phenols such as HCA-HQ, HCA-NQ, PPQ, diphenylphenylphosphino-1,4-dihydroxynaphthalene, CPHO-HQ, and CPHO-HQ, but they are not Limited to these. Further, these phosphorus-containing phenol compounds may be used in combination of two or more kinds.

Further, the phosphorus-containing phenol compound may be a compound of the above formula (3), Specifically, for example, a phosphorus compound having an active hydrogen group directly bonded to a phosphorus atom such as HCA or diphenylphosphine is obtained by a reaction with an anthracene such as 1,4-benzoquinone or 1,4-naphthoquinone. The synthesis method is shown in Patent Document 7, Patent Document 8, and Non-Patent Document 1, but the present invention is not limited thereto. Further, a phosphorus-containing phenol compound can also be synthesized in a phosphorus-containing epoxy resin.

The invention is characterized in that the specific content is dissolved in a specific phosphorus-containing epoxy resin The phosphorus phenol compound, which is a state in which the phosphorus-containing phenol compound is dissolved in the phosphorus-containing epoxy resin, means that no solid of the phosphorus-containing phenol resin is observed in the phosphorus-containing epoxy resin at room temperature. Specifically, it means a state in which, when the phosphorus-containing epoxy resin composition is a solid, defoaming is performed by heating and melting, and defoaming is directly performed in the case of a liquid, and in an environment of 23 ° C, 20 is used. Double microscope It was confirmed that the solid derived from the phosphorus-containing phenol compound did not precipitate. Further, it means that when the phosphorus-containing epoxy resin composition is dissolved in a solvent, it is confirmed that the solid derived from the phosphorus-containing phenol compound is not precipitated by a microscope observed at 20 times directly at room temperature.

There is no specific method for dissolving a phosphorus-containing phenol compound in a phosphorus-containing epoxy resin. In addition, it is possible to mix a previously synthesized or commercially available phosphorus-containing phenol compound in a phosphorus-containing epoxy resin, or obtain a target phosphorus-containing epoxy by synthesizing a phosphorus-containing phenol compound in a phosphorus-containing epoxy resin. Resin composition. Further, it is also possible to dissolve the remaining phosphorus compound while synthesizing the phosphorus-containing epoxy resin by reacting the phosphorus-containing phenol compound with the epihalohydrin.

The phosphorus-containing phenol compound can be dissolved in the phosphorus-containing epoxy resin in the absence of a solvent or a solvent in combination, and can be dissolved by heating and stirring to such an extent that no reaction between the phosphorus-containing epoxy resin and the phosphorus-containing phenol compound occurs.

In the case of synthesizing a phosphorus-containing phenol compound in a phosphorus-containing epoxy resin, the phosphorus compound of the above formula (3) and a ruthenium compound may be added to the phosphorus-containing epoxy resin to carry out a reaction. In the reaction, a solvent is preferably used in combination. The solvent which can be used is preferably an aprotic solvent, and examples thereof include toluene, xylene, methanol, ethanol, 2-butoxyethanol, dialkyl ether, glycol ether, propylene glycol monomethyl ether, and Alkane, etc. These reaction solvents may be used singly or in combination of two or more kinds.

The epoxy resin composition in which the phosphorus-containing phenol compound is dissolved in the phosphorus-containing epoxy resin can be adjusted by adjusting the reaction ratio and reaction conditions when the phosphorus-containing phenol compound is reacted with the epihalohydrin.

Phosphorus-containing phenol compounds lack solubility in organic solvents, so whether by any method, if the amount of solvent used is too large, the phosphorus-containing phenol compound is not dissolved in the phosphorus-containing epoxy tree. The amount of the organic solvent is preferably 50% by mass or less based on the total mass of the phosphorus-containing epoxy resin composition.

Moreover, the temperature at which the dissolution is carried out in any of the methods is preferably from 100 to 200 ° C. More preferably 120~160 °C. When the dissolution temperature is low, the dissolution rate becomes slow. When the dissolution temperature is high, the reaction and dissolution of the phenol group and the epoxy group proceed together, and the viscosity becomes high, so that it becomes difficult to handle.

Also, regarding the phosphorus-containing phenol compound used herein, relative to the phosphorus-containing epoxy tree 100 parts by mass of the fat must be 5 to 45 parts by mass, and further preferably 10 to 45 parts by mass from the viewpoint of flame retardancy. When the phosphorus-containing phenol compound is less than 5 parts by mass, in order to obtain flame retardancy, it is necessary to increase the phosphorus content of the phosphorus-containing epoxy resin, and the viscosity of the resin becomes high, so that dissolution of the phosphorus-containing phenol resin becomes difficult. When the phosphorus-containing epoxy resin has a low phosphorus content, it is easily dissolved, but flame retardancy cannot be obtained. In the case where there are many phosphorus-containing phenol compounds, there are defects which are not completely dissolved.

Furthermore, when it is called the phosphorus-containing epoxy resin composition of the present invention, as long as there is no special In other words, it is used in the following meanings: a phosphorus-containing epoxy resin having a structure of the general formula (1) and a phosphorus-containing epoxy resin composed of the phosphorus-containing phenol compound represented by the general formula (2). And (a) consisting of a phosphorus-containing epoxy resin having a structure of the formula (1), a phosphorus-containing phenol compound represented by the formula (2), and an epoxy resin (B) (b), a phosphorus-containing epoxy resin composition comprising a phosphorus-containing epoxy resin having the structure of the formula (1), a phosphorus-containing phenol compound represented by the formula (2), and a curing agent (C) (c1), and a phosphorus-containing epoxy resin having a structure of the formula (1), a phosphorus-containing phenol compound represented by the formula (2), an epoxy resin (B), and a curing agent (C) The phosphorus-containing epoxy resin composition (c2), when exemplified in the context of the art, represents any of the phosphorus-containing epoxy resin compositions. In addition, the phosphorus-containing epoxy resin composition is further blended In the case of something, the total of the components constituting each of the phosphorus-containing epoxy resin compositions is used as a reference. That is, when the phosphorus-containing epoxy resin composition (a) is further blended with a certain substance, the phosphorus-containing epoxy resin having the structure of the general formula (1) and the phosphorus-containing phenol represented by the general formula (2) The total amount of the compound 2 component is a standard, and when the phosphorus-containing epoxy resin composition (c2) is further blended with a certain substance, the phosphorus-containing epoxy resin having the structure of the general formula (1), the general formula (2) The total amount of the phosphorus-containing phenol compound, the epoxy resin (B), and the curing agent (C) 4 component is based on the total amount.

The phosphorus-containing epoxy resin composition (a) of the present invention may be further added with an epoxy resin (B). In this case, the method of mixing the epoxy resin (B) is not particularly limited and can be carried out by a method generally used. Further, in the case of heating and mixing, it is preferably carried out at 200 ° C or lower, and more preferably at 160 ° C or lower. When the mixing temperature is 200 ° C or higher, the reaction of the epoxy group in the phosphorus-containing epoxy resin composition (b) occurs, and the viscosity becomes high, which makes it difficult to handle.

As the epoxy resin (B) used here, and when synthesizing the phosphorus-containing epoxy resin The epoxy resin to be used has at least 1.5 epoxy groups in the molecule, and more preferably two or more. These epoxy resins may be used singly or in combination of two or more.

At this time, regarding the amount of the epoxy resin (B), in terms of flame retardancy, The phosphorus content of the phosphorus-containing epoxy resin composition (b) to which the epoxy resin (B) is added is preferably 2% by mass or more. If the phosphorus content in the phosphorus-containing epoxy resin composition (b) is small, there is a possibility that the flame retardancy is not exhibited.

As the curing agent (C) which can be used in the phosphorus-containing epoxy resin composition [(a) or (b)] of the present invention, a known public compound for an epoxy resin can be used. Specifically, for example, a neighbor can be cited. Hydroxybenzenes such as hydroquinone, resorcinol, hydroquinone, binaphthols, biphenols, trisphenols, bisphenol A, bisphenol F, bisphenol S, trishydroxyphenylmethane, three Hydroxyphenylethane, Shonol BRG-555 (phenol novolak resin manufactured by Showa Denko Co., Ltd.), cresol novolak resin, alkylphenol novolak resin, aralkyl phenol novolac resin, containing three Ring phenol novolac resin, biphenyl aralkyl phenol resin, RESITOP TPM-100 (manufactured by Qunrong Chemical Industry Co., Ltd., trishydroxyphenylmethane novolak resin), aralkyl naphthalene diphenol resin is equal to one molecule a compound having two or more phenolic hydroxyl groups, an anthraquinone adipic acid, an anthraquinone azelate or the like, an imidazole compound and a salt thereof, a dicyandiamide, an aminobenzoic acid ester, and An aliphatic amine such as ethyltriamine, tri-ethyltetramine, tetraethylamamine, m-xylylenediamine or isophorone diamine, diaminodiphenylmethane An aromatic amine such as diaminodiphenyl hydrazine or diaminoethyl benzene, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, and cis-butene Diacid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, etc. An acid anhydride or the like, 2 imidazoles such as methylimidazole, 2 ethyl 4-methylimidazole, and 2 phenylimidazole, etc. Two or more kinds of these hardeners are used in combination. Regarding the amount of the hardener (C) used, the epoxy equivalent contained in the phosphorus-containing epoxy resin composition [(a) or (b)] is subtracted from the phosphorus contained in the phosphorus-containing epoxy resin composition. When the value of the active hydrogen equivalent of the phenol compound is 1 equivalent, the functional group of the curing agent (C) is preferably in the range of 0.1 to 1.3 equivalents, more preferably 0.2 to 1.0 equivalent. When the equivalent of the functional group of the curing agent is small, the curing reaction of the epoxy group is not sufficiently carried out, so that it cannot be obtained as a cured product. If there are many, the unreacted curing agent remains, so that the cured product cannot be sufficiently obtained. The mechanical properties are the same.

For the phosphorus-containing epoxy resin composition of the present invention, adjusting fluidity or viscosity, etc. In the case of the case, the diluent can be used in a range that does not impair the physical properties. The diluent is preferably reactively diluted The agent may also be a non-reactive diluent. Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl epoxidized ether, 2-ethylhexyl epoxidized propyl ether and phenyl epoxidized propyl ether, and resorcinol epoxidized ether. , dipentyl epoxidized ethers such as neopentyl glycol epoxidized ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, new A polyfunctional glycidyl ether such as pentaerythritol polyglycidyl ether. Examples of the non-reactive diluent include benzyl alcohol, diethylene glycol butyl ether, and pine oil. The diluent is preferably 30 parts by mass or less based on 100 parts by mass of the phosphorus-containing epoxy resin composition. When the amount of the diluent added is large, in the case of the non-reactive diluent, there is a bleed out of the hardened material, and in the case of the reactive diluent, the hardening reaction does not sufficiently proceed to bleed out.

Moreover, it is possible to use hardening as needed in the phosphorus-containing epoxy resin composition of the present invention. Into the agent. 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. The hardening accelerators are preferably different depending on the type of the epoxy resin to be used, the type of the epoxy resin curing agent to be used, the molding method, the curing temperature, and other desired characteristics, and are preferably 100 parts by mass based on the phosphorus-containing epoxy resin composition. It is in the range of 0.01 to 10 parts by mass.

The composition of the phosphorus-containing epoxy resin of the present invention can also be used without impairing the characteristics It is blended with other thermosetting resins and thermoplastic resins. For example, phenol resin, acrylic resin, petroleum resin, enamel resin, scented samarium-indene resin, phenoxy resin, polyurethane, polyester, polyamide, polyimine, polyamidimide, poly Ether quinone imine, polyether oxime, polyfluorene, polyether ether ketone, polyphenylene sulfide, polyvinyl formal, styrene maleic acid resin, etc., but it is not limited to these. It is preferable that the thermosetting resin or the thermoplastic resin is relative to the phosphorus-containing epoxy tree. The fat composition is blended in an amount of not more than 50 parts by mass. When the blending amount exceeds 50 parts by mass, the phosphorus content in the cured product is lowered, and sufficient flame retardancy cannot be obtained.

Regarding the phosphorus-containing epoxy resin composition of the present invention, inorganic filling may be blended as needed Agent, organic filler. Examples of the filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, boehmite, talc, calcined talc, clay, kaolin, mica, calcium carbonate, and citric acid. Calcium, calcium hydroxide, magnesium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, titanium oxide, glass powder, silica hollow sphere, carbon, carbon fiber, glass fiber, alumina fiber, two Cerium oxide-alumina fiber, tantalum carbide fiber, polyester fiber, cellulose fiber, aromatic polyamide fiber, synthetic fiber, ceramic fiber, and the like. The filler is preferably 1 to 80 parts by mass based on 100 parts by mass of the phosphorus-containing epoxy resin composition. If it is small, it does not exhibit the characteristics of an inorganic filler or an organic filler. If it is large, it will become brittle after hardening, and the cured product cannot obtain sufficient mechanical properties.

Regarding the phosphorus-containing epoxy resin composition of the present invention, it may be further blended as needed. Various additives such as an alkane coupling agent, an antioxidant, a releasing agent, an antifoaming agent, an emulsifier, a thixotropic imparting agent, a smoothing agent, a flame retardant, and a pigment. These additives are preferably in the range of 0.01 to 20% by mass based on the total mass of the resin composition.

The phosphorus-containing epoxy resin composition of the present invention can be obtained by using a known epoxy resin group. The method of the same thing is hardened to form a cured product. The phenolic compound dissolved in the phosphorus-containing epoxy resin reacts with the epoxy group of the phosphorus-containing epoxy resin or the epoxy resin (B) to cause hardening. However, the hardening method can be carried out in the same manner as the known epoxy resin composition, and the method inherent to the resin composition of the present invention is not required.

The phosphorus-containing epoxy resin composition of the present invention can be impregnated into a fibrous substrate by A prepreg used in a printed wiring board or the like is produced. As the fibrous base material, an inorganic fiber such as glass or a woven fabric or a non-woven fabric of an organic fiber such as polyester, polyacryl, polyacryl, polyimine or kewei may be used, but the invention is not limited thereto. The method for producing the prepreg from the phosphorus-containing epoxy resin composition of the present invention is not particularly limited, and is, for example, immersed in a resin varnish prepared by adjusting the viscosity of the phosphorus-containing epoxy resin composition with a solvent. The resin is obtained by heat-drying and semi-curing (B-stage) the resin component. For example, it can be dried by heating at 100 to 200 ° C for 1 to 40 minutes. Here, the amount of the resin in the prepreg is preferably 30 to 80% by mass based on the resin component.

Moreover, in order to harden the prepreg produced by the above-mentioned method, the hardening method of the laminated board currently used at the time of manufacture of a printed wiring board can be used, It is not limited to this. For example, when a prepreg is used to form a laminate, one or a plurality of prepreg layers are placed, and a metal foil is placed on one side or both sides to form a laminate, and the laminate is heated and pressurized to form a laminate. Chemical. Here, as the metal foil, a single metal such as copper, aluminum, brass, or nickel, or a composite metal foil can be used. The prepreg can be obtained by pressurizing and heating the laminate prepared here to obtain a laminate, by setting the temperature to 160 to 220 ° C, the pressure to 50 to 500 N/cm ² , and the heating and pressing time. Set to 40 to 240 minutes to obtain the target hardened material. If the heating temperature is low, the hardening reaction does not proceed sufficiently, and if it is high, the phosphorus-containing epoxy resin composition begins to decompose. Moreover, when the pressurization pressure is low, there is a possibility that the resin flows and the cured product of a desired thickness cannot be obtained. Further, when the heating and pressing time is short, there is a possibility that the curing reaction does not proceed sufficiently, and if it is long, there is a possibility that thermal decomposition of the phosphorus-containing epoxy resin composition in the prepreg may occur. Therefore, it is preferable to manage under the above conditions.

Since the phosphorus-containing epoxy resin composition of the present invention has a high phosphorus content, it is excellent Since it is inflammable and has a low viscosity, it has good impregnation properties to a fibrous substrate such as glass cloth, and is excellent in workability. It is known that the flame-retardant or heat-resistant and cured adhesive of the phosphorus-containing epoxy resin is excellent, and it is used as a sealing material for electric-electronic parts, a copper-clad laminate, an insulating coating, a flame retardant coating, a composite material, and an insulating flame retardant. Materials such as agents are useful.

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention It is not limited to the following examples. In addition, unless otherwise indicated, the part represents "parts by mass", and % means "mass%". Further, the analysis methods and measurement methods of the examples and comparative examples were carried out by the following methods.

Epoxy equivalent: according to JIS K7236.

Phenolic hydroxyl equivalent: To the sample, THF containing 4% methanol was added, and 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 was determined from the weight of the sample per hydroxy group of the hydroxyl group based on the calibration curve obtained by the same measurement method.

Viscosity: The measurement was carried out at 25 ° C using a B-type viscometer TVB-10H manufactured by Toki Sangyo Co., Ltd.

Phosphorus-containing rate: sulfuric acid, hydrochloric acid, and perchloric acid are added to the sample, and heated to perform wet ashing, and all phosphorus atoms are made into orthophosphoric acid. The metavanadate and the molybdate were reacted in an acidic sulfuric acid solution, and the absorbance of the resulting phosphovanadomolybdic acid complex at 420 nm was measured, and the phosphorus atom content determined by a calibration curve prepared in advance was expressed in %. The phosphorus content of the laminate is expressed in terms of the content of the resin component relative to the laminate.

Glass transfer temperature: Measured according to IPC-TM650 2.4.25c.

Flame retardancy: The measurement was carried out in accordance with UL (Underwriter Laboratorics) standards. Evaluation V-0, V-1, V-2 records. Further, the total of the five residual flame times is recorded as the total of the residual flame time.

Solubility: In the case of a solid, defoaming by heating and melting, direct defoaming in the case of a liquid, and using a microscope of 20 times in an environment of 23 ° C, confirming that the solid derived from the phosphorus-containing phenol compound is not Precipitate. The ○ indicates that no precipitate is present, and the x indicates the precipitater.

Example 1

57.7 parts of a phenol novolak type epoxy resin as an epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a product of a four-neck separable flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen inlet tube) Epotohto YDPN-638) and 42.3 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA) as a phosphorus compound at 160 ° C The reaction was carried out for 5 hours, whereby a phosphorus-containing epoxy resin having an epoxy equivalent of 766 g/eq and a phosphorus content of 6.0% was obtained. 10 parts of 10-(1,4-dihydroxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene (manufactured by Sanko Co., Ltd., trade name HCA-NQ) was added as a phosphorus-containing phenol compound. The mixture was stirred at 120 ° C for 2 hours, whereby a target phosphorus-containing epoxy resin composition was obtained. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 6.2%. The phosphorus-containing epoxy resin composition is diluted with a methyl ethyl ketone (hereinafter referred to as MEK) to a solid content of 70%. The viscosity of the phosphorus-containing epoxy resin composition varnish is 9800 mPa. s.

Example 2

The epoxy resin was changed to 66.2 parts of YDPN-638, and the phosphorus compound was changed to 33.8 parts of HCA, and the phosphorus-containing phenol compound was changed to 20 parts of 10-(2,5-dihydroxyphenyl)-10H-9. The same operation as in Example 1 was carried out except that oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA-HQ) was obtained, and an epoxy equivalent of 460 g/eq was obtained. After the phosphorus-containing epoxy resin having a phosphorus ratio of 4.2%, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. Place The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 5.6%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70%. The viscosity of the phosphorus-containing epoxy resin composition varnish is 1040 mPa. s.

Example 3

The same operation as in Example 1 was carried out except that the epoxy resin was changed to 71.8 parts of YDPN-638, and the phosphorus compound was changed to 28.2 parts of HCA, and the phosphorus-containing phenol compound was changed to 45 parts of HCA-NQ. After obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 363 g/eq and a phosphorus content of 4.0%, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 5.3%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70%, and the viscosity of the phosphorus-containing epoxy resin composition varnish is 1010 mPa. s.

Example 4

The same operation as in Example 1 was carried out except that the epoxy resin was changed to 84.5 parts of YDPN-638, and the phosphorus compound was changed to 15.5 parts of HCA, and the phosphorus-containing phenol compound was changed to 40 parts of HCA-NQ. After obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 247 g/eq and a phosphorus content of 2.2%, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.9%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70%, and the viscosity of the phosphorus-containing epoxy resin composition varnish is 530 mPa. s.

Example 5

As an epoxy resin, it was changed to 63.8 parts of YDPN-638 and 10 parts of bisphenol F type liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name Epotohto YDF-170) as The same procedure as in Example 1 was carried out to obtain an epoxy equivalent of 355 g/eq, except that the phosphorus compound was changed to 15.6 parts of HCA and 10.6 parts of HCA-HQ, and the phosphorus-containing phenol compound was changed to 5 parts of HCA-NQ. After the phosphorus-containing epoxy resin having a phosphorus content of 3.2%, the HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.5%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70% to form a phosphorus-containing epoxy resin composition varnish having a viscosity of 650 mPa. s.

Example 6

As an epoxy resin, it was changed to 55.6 parts of o-cresol novolak type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name Epotohto YDCN-700-7) and 20 parts of YDF-170 as phosphorus compounds. An epoxy equivalent of 365 g/eq and a phosphorus content were obtained by the same operation as in Example 1 except that 16.4 parts of HCA and 80 parts of HCA-NQ were changed to 8 parts of HCA-HQ as the phosphorus-containing phenol compound. After the 3.0% phosphorus-containing epoxy resin, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.5%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70% to form a phosphorus-containing epoxy resin composition varnish having a viscosity of 600 mPa. s.

Comparative example 1

100 parts of YDPN-638 and 28 parts of HCA-NQ were added to a four-neck separable flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen introduction tube, and the mixture was stirred at 120 ° C, but even after stirring for 6 hours, Can't dissolve completely.

Comparative example 2

The epoxy resin was changed to 88 parts of YDPN-638, and the phosphorus compound was changed to 12 parts of HCA, and the phosphorus-containing phenol compound was changed to 4 parts of HCA-HQ, and other methods were carried out and carried out. In the same manner as in Example 1, after obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 226 g/eq and a phosphorus content of 1.7%, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 2.0%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70% to form a phosphorus-containing epoxy resin composition varnish having a viscosity of 500 mPa. s.

Comparative example 3

The same operation as in Example 1 was carried out except that the epoxy resin was changed to 88 parts of YDPN-638, and the phosphorus compound was changed to 12 parts of HCA, and the phosphorus-containing phenol compound was changed to 13 parts of HCA-HQ. After obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 226 g/eq and a phosphorus content of 1.7%, the crystal of HCA-NQ was not dissolved, and the desired phosphorus-containing epoxy resin composition could not be obtained.

Comparative example 4

The same operation as in Example 1 was carried out except that the epoxy resin was changed to 49.3 parts of YDPN-638, and the phosphorus compound was changed to 50.7 parts of HCA, and the phosphorus-containing phenol compound was changed to 8 parts of HCA-HQ. After obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 2285 g/eq and a phosphorus content of 7.2%, the crystal of HCA-NQ was not dissolved, and the desired phosphorus-containing epoxy resin composition could not be obtained.

Dissolving the phosphorus-containing epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 The solution is shown in Table 1.

Example 7

75 parts of the phosphorus-containing epoxy resin composition obtained in Example 3 was added as an epoxy resin (B) 25 parts of triphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name EPPN-501H), phenol novolak resin as hardener (C) (manufactured by Showa Denko Co., Ltd., trade name Shonol BRG -557) 25.6 parts, 0.1 parts of 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., trade name Curezol 2E4MZ) as a curing catalyst, and a non-volatile content of 50% using MEK to obtain a resin varnish . The obtained resin varnish was impregnated into a glass cloth (model investigation), and dried at 150 ° C for 10 minutes, thereby obtaining a prepreg. 4 pieces of the obtained prepreg and copper foil (manufactured by Mitsui Mining & Mining Co., Ltd., trade name 3EC-III, thickness 35 μm) were superposed, and the temperature was 130 MPa × 15 minutes + 190 ° C × 80 minutes at 2 MPa. The pressure was vacuum pressed to obtain a cured product of a 0.5 mm thick laminated board.

Example 8

70 parts of the phosphorus-containing epoxy resin composition obtained in Example 3, styrene-modified phenol novolac type epoxy resin as epoxy resin (B) (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name TX-1210-90) was set to 30 parts, and the dicyandiamide (DICY) as the curing agent (C) was set to 2.0 parts, and the 2E4MZ as the curing catalyst was set to 0.9 parts, and the examples and the examples were used. 7 The same method is used to obtain a cured product of a prepreg and a laminate.

Example 9

For 70 parts of the phosphorus-containing epoxy resin composition obtained in Example 3, TX-1210-90 as the epoxy resin (B) was set to 30 parts, and BRG-557 as the curing agent (C) was set to 19.9. A prepreg and a cured product of a laminate were obtained in the same manner as in Example 7 except that 2E4MZ as a curing catalyst was changed to 0.9 parts.

Example 10

85 parts of the phosphorus-containing epoxy resin composition obtained in Example 3, which will be used as the epoxy resin (B) The bisphenol A type solid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name Epotohto YD-903N) is set to 15 parts, and the DICY as the curing agent (C) is set to 1.3 parts, which will serve as a hardening contact. A prepreg and a cured product of a laminate were obtained in the same manner as in Example 7 except that the medium 2E4MZ was set to 0.9 parts.

Comparative Example 5

For 70 parts of the phosphorus-containing epoxy resin composition obtained in Comparative Example 2, the TX-1210-90 as the epoxy resin (B) was set to 30 parts, and the DICY as the curing agent (C) was set to 4.4 parts. A prepreg and a cured product of a laminate were obtained in the same manner as in Example 7 except that 2E4MZ as a curing catalyst was changed to 0.9 parts.

Comparative Example 6

Adding 23.5 parts of HCA, 4.3 parts of 1,4-naphthoquinone, and 100 parts of toluene to a separable flask made of glass equipped with a stirring device, a thermometer, a condenser, and a nitrogen introduction device, and performing at 75 ° C for 30 minutes After stirring, the dehydration reaction was carried out at 110 ° C for 90 minutes, and then 72.2 parts of YDPN-638 was added, and the temperature was raised to remove toluene. Thereafter, 0.01 part of triphenylphosphine (TPP) as a catalyst was added, and the mixture was reacted at 160 ° C for 4 hours to obtain a phosphorus-containing epoxy resin having an epoxy equivalent of 348 g/eq and a phosphorus content of 1.5%. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70%. The viscosity of the phosphorus-containing epoxy resin composition varnish is 1730 mPa. s.

70 parts of the obtained phosphorus-containing epoxy resin, 30 parts of TX-1210-90 as the epoxy resin (B), and 24.3 parts of BRG-557 as the curing agent (C), A cured product of the prepreg and the laminated sheet was obtained in the same manner as in Example 7 except that 2E4MZ was used as the curing catalyst.

Comparative Example 7

64.1 parts of YDPN-638 as an epoxy resin and 20.9 parts of HCA and 15 parts of HCA-HQ as a phosphorus compound were added to a four-port separable flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen introduction tube. The reaction was carried out at 160 ° C for 5 hours, whereby a phosphorus-containing epoxy resin having an epoxy equivalent of 444 g/eq, a phenolic hydroxyl equivalent of 1750 g/eq, and a phosphorus content of 3.0% was obtained. The phosphorus-containing epoxy resin composition is diluted with MEK to a solid content of 70%. The viscosity of the phosphorus-containing epoxy resin composition varnish is 440 mPa. s.

For 70 parts of the obtained phosphorus-containing epoxy resin, the TX-1210-90 as the epoxy resin (B) was set to 30 parts, and the BRG-557 as the curing agent (C) was set to 29.4 parts, which was used as the hardening. A cured product of a prepreg and a laminate was obtained in the same manner as in Example 7 except that 2E4MZ of the catalyst was changed to 0.9 parts.

The physical properties of the laminates of Examples 7 to 10 and Comparative Examples 5 to 7 are shown in Table 2.

Adding phosphorus-containing phenol resin to phosphorus-containing epoxy resin as shown in the examples The composition was confirmed to be soluble in the resin under specific conditions to obtain a uniform composition. It was confirmed that these compounds have sufficiently low viscosity and good handleability. Further, it was confirmed that the obtained cured product was sufficiently flame retardant.

On the other hand, in Comparative Example 1, an attempt was made to dissolve the phosphorus-containing phenol resin in the absence of phosphorus. In the epoxy resin, it was confirmed that the phosphorus-containing phenol compound was not completely dissolved and was in a state of being uneven.

In Comparative Example 2, the phosphorus-containing phenol resin was dissolved using a phosphorus-containing epoxy resin, but contained The phosphorus-containing epoxy resin composition has a phosphorus content of less than 2%, so that the amount of the soluble phosphorus-containing phenol resin is small, and the laminate using the phosphorus-containing epoxy resin composition has low flame retardancy (Comparative) Example 5). Further, when the phosphorus-containing phenol resin was further dissolved, it was not completely dissolved. If the amount was in Comparative Example 3, the precipitation of the phosphorus-containing phenol resin was confirmed by visual observation.

In Comparative Example 4, the phosphorus-containing phenol resin was dissolved using a phosphorus-containing epoxy resin, but contained Since the phosphorus content in the phosphorus epoxy resin composition exceeds 7%, the viscosity of the phosphorus-containing epoxy resin becomes high, and the phosphorus-containing phenol resin cannot be dissolved.

Comparative Example 6 is a review of a laminate using a phosphorus-containing epoxy resin of Patent Document 2. The price is slightly inflammable and the heat resistance is slightly worse.

Comparative Example 7 is a review of a laminate using a phosphorus-containing epoxy resin of Patent Document 4. The price is slightly inflammable and the heat resistance is slightly worse.

It can be seen from the examples and comparative examples that the specific phosphorus-containing epoxy resin is dissolved in a specific The phosphorus-containing phenol compound is low in viscosity, excellent in workability, and high in flame retardancy. Further, in the composition of the present invention, it is understood that even if the epoxy resin (B) having improved heat resistance, dielectric constant, and adhesion is blended, flame retardancy can be obtained, and dielectric properties are particularly lowered.

Claims (7)

A phosphorus-containing epoxy resin composition which dissolves 5 to 45 masses with respect to 100 parts by mass of a phosphorus-containing epoxy resin in a range of 2 to 7 mass% with respect to a structure having a structure of the following formula (1) a phosphorus-containing phenol compound represented by the following formula (2), which is not precipitated at room temperature, (wherein R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a cyclic ring together with a phosphorus atom; i represents 0 or 1) (wherein R ₃ and R ₄ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may be cyclic together with a phosphorus atom; n represents 0 or 1; and A represents an aromatic hydrocarbon having 6 to 20 carbon atoms; Three base (arenetriyl). For example, the phosphorus-containing epoxy resin composition of claim 1 is made by blending an epoxy resin (B). The phosphorus-containing epoxy resin composition according to the second aspect of the patent application has a phosphorus content of 2% by mass or more. The phosphorus-containing epoxy resin composition according to any one of claims 1 to 3, which is obtained by blending a hardener (C). A prepreg obtained by impregnating a fibrous substrate with a phosphorus-containing epoxy resin composition according to any one of claims 1 to 4. A hardened material which is a phosphorus-containing epoxy tree of any one of claims 1 to 4. The lipid composition is hardened. A hardened material obtained by hardening a prepreg according to item 5 of the patent application.