JP2013103975A - Phosphorus-containing phenol resin and production method thereof, the resin composition, cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high quality flame-retardant phosphorus-containing phenol resin suitable for a prepreg, a copper-clad laminate used for electronic circuit board; a film material, sealing material, molding material, casting material, adhesive and electric insulation coating material used for electronic parts; a composite requiring flame retardancy; and powder coating material, or the like, while reducing cost; and provide the phenol resin composition.SOLUTION: This phosphorus-containing phenol resin is obtained by reacting phosphorus-containing compounds (B) essentially containing a phosphorus-containing phenol compound (b) expressed by general formula (1) and two or more functional phosphorus-free phenol compounds (c), with an epoxy resin (a) having ≥1.8 epoxy groups in average in a molecule, through two step reaction stages, where the first step reaction stage includes a precursor reaction of reacting the epoxy resin (a) with the phosphorus-containing compounds (B). In formula, A represents a 6-20C arylene group and/or triyl group; γ denotes 0 or 1; Rand Rare each represents a 1-6C hydrocarbon group which may be the same or different from each other, or may form a ring together with the phosphorus atom.

Description

The present invention relates to a phosphorus-containing phenol resin having flame retardancy, a method for producing the same, a curable resin composition containing the phosphorus-containing phenol resin, and a cured product thereof.

Phenolic resins utilize their excellent heat resistance, adhesiveness, mechanical properties, electrical properties, etc., and are used as molding materials for various substrates, binders for friction materials, binders for abrasives, adhesives for wood, and molds. Widely used as binders, laminate binders, coating agents, epoxy resin curing agents and the like.

In particular, when used in electrical and electronic equipment as a laminated material, it is strongly required to impart flame retardancy in order to prevent combustion in a fire and control smoke generation. Conventionally, as a flame retardant method for resin for laminates, brominated flame retardants, nitrogen flame retardants and phosphorus flame retardants alone or in combination, and inorganic flame retardant aids are used in combination with the flame retardant alone or in combination. Flame retardant systems were mainstream. However, in recent years, the use of brominated flame retardants has been avoided due to environmental problems. In addition, when red phosphorus is used as the additive type phosphorus flame retardant, safety is insufficient, and when a phosphoric acid compound is used, there is a problem of bleeding out on the surface of the cured product. Further, when phosphoric acid esters are used, there is a problem that solder heat resistance and solvent resistance are lowered. Therefore, development of a non-halogen reaction type flame retardant that can obtain flame retardancy without using these additive type flame retardants is required.

On the other hand, the epoxy resin curing agent has the same problems as described above. For example, 2-diphenylphosphinyl hydroquinone (trade name PPQ manufactured by Hokuko Chemical Co., Ltd.) or 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Stock Co., Ltd.) When a phosphorus-containing phenolic compound such as the product name HCA-HQ) manufactured by the company is used, a highly flame-retardant epoxy resin cured product is obtained. These phosphorus-containing phenolic compounds are soluble in solvents and compatible with epoxy resins. However, when used alone as a curing agent, it settles without dissolving in the epoxy resin varnish, so that it is not practical for use as a laminated material. In order to solve this problem, in Patent Documents 1 and 2, in consideration of dispersibility, a first-stage reaction in which an epoxy resin and a phosphorus-containing phenol compound are reacted in advance is performed, and a part of the reaction is made a phosphorus-containing epoxy resin. There is disclosure. However, there are problems such as low adhesion, and the solvent solubility of the resin is not sufficiently satisfactory, such as using a high boiling point solvent as the solvent for the varnish. Patent Document 3 also proposes a phosphorus-containing phenolic resin with improved compatibility with an epoxy resin. However, since cyclohexanone having a high boiling point is used as a reaction solvent, the solvent is completely removed in the production process of the laminate. This is difficult, and there is a risk that the adhesiveness and heat resistance reliability of the cured epoxy resin will deteriorate.

JP-A-8-188638 JP 2000-256537 A JP2003-40969A

The object of the present invention is to provide flame retardancy without using an additive-type flame retardant, and also has good solubility in various organic solvents, sealing materials, molding materials, laminates, casting materials, Provided a phosphorus-containing phenolic resin suitable for adhesives, insulating paints and the like and a method for producing the same, and cured a resin composition containing the phosphorus-containing phenolic resin, thereby providing excellent flame retardancy, heat resistance reliability, and adhesiveness. A cured product is provided.

That is, the present invention
(1) Phosphorus-containing compounds (B) containing, as an essential component, a phosphorus-containing phenol compound (b) represented by the general formula (1) in an epoxy resin (a) having an average of 1.8 or more epoxy groups in one molecule ), And a phosphorus-containing phenolic compound (c) having two or more functional groups, which are obtained by reacting in a two-step reaction process, the epoxy resin (a) and The manufacturing method of the phosphorus containing phenol resin characterized by including the precursor reaction which makes phosphorus containing compounds (B) react.

（式中Ａは炭素数６から２０のアリーレン基及び／またはトリイル基を表す。式中γは０または１を表し、Ｒ_１及びＲ_２は炭素数１から６の炭化水素基を表し、同一であっても異なっていてもよく、リン原子と共に環状になっていてもよい。）

(In the formula, A represents an arylene group and / or triyl group having 6 to 20 carbon atoms. In the formula, γ represents 0 or 1, R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, and are the same. Or may be different, and may be cyclic with a phosphorus atom.)

(2) The said (1) description whose phenolic hydroxyl group of phosphorus containing phenolic compound (b) is 0.3 mol to 1.5 mol with respect to 1 mol of epoxy groups of an epoxy resin (a) at the said 1st reaction process. Of producing a phosphorus-containing phenolic resin.

(3) The phosphorus-containing phenol compound (b) used in the first-stage reaction step is 50% to 100% of all the phosphorus-containing phenol compounds (b) used in the production of the phosphorus-containing phenol resin ( The manufacturing method of the phosphorus containing phenol resin of 1) or (2) description.

(4) The phosphorus-containing phenol according to any one of (1) to (3), wherein a reaction rate of an epoxy group of the epoxy resin (a) in the first-stage reaction step is 30% to 95%. Manufacturing method of resin.

(5) A phosphorus-containing phenol resin obtained by reacting a bifunctional or higher phosphorus-free phenol compound (c) as a second-stage reaction after completion of the first-stage reaction step, the epoxy resin (a) Any of (1) to (4) above, wherein the total phenolic hydroxyl group of the phosphorus-containing phenol compound (b) and the phosphorus-free phenol compound (c) is 1.5 mol to 4.5 mol with respect to 1 mol of the epoxy group of 2. A method for producing a phosphorus-containing phenol resin according to item 1.

(6) A phosphorus-containing phenol resin obtained by the production method according to any one of (1) to (5) above.

(7) A phosphorus-containing phenol resin composition comprising the phosphorus-containing phenol resin according to (6) above.

(8) Hardened | cured material which hardened the phosphorus containing phenol resin composition as described in said (7).

According to the present invention, phosphorus-containing compounds containing as an essential component an epoxy resin (a) having an average of 1.8 or more epoxy groups in one molecule and a phosphorus-containing phenol compound (b) represented by the general formula (1) (B) is reacted in the first stage, and in the second stage, the phosphorus-free phenol compound (c) is reacted to easily produce a phosphorus-containing phenol resin having solubility in various organic solvents. it can.

The production method of the phosphorus-containing phenol resin of the present invention comprises, as a raw material, an epoxy resin (a) having an average of 1.8 or more epoxy groups in one molecule and a phosphorus-containing phenol compound (b) represented by the general formula (1). The phosphorus-containing compounds (B) contained as essential and the phosphorus-free phenol compound (c) having two or more functions are essential, and the epoxy resin (a) and the phosphorus-containing compounds (B) are reacted in the first stage. Including the precursor reaction, the second stage has a two-stage reaction process in which phenol compounds containing phosphorus-free phenol (c) as an essential component are reacted.

Examples of the epoxy resin (a) used as a raw material include Epototo YD-128, Epototo YD-8125 (BPA type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDF-170, Epototo YDF-8170 (Nippon Steel Chemical Co., Ltd.) BPF type epoxy resin made by company), YSLV-80XY (tetramethylbisphenol F type epoxy resin made by Nippon Steel Chemical Co., Ltd.), Epototo YDC-1312 (hydroquinone type epoxy resin), jER YX4000H (Mitsubishi Chemical Corporation biphenyl type epoxy) Resin), Epototo YDPN-638 (Phenol Novolak type epoxy resin manufactured by Nippon Steel Corp.), Epotot YDCN-701 (Cresol Novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1201 ( Nippon Steel Chemical Co., Ltd. bisphenol fluorene type epoxy resin), TX-0710 (Nippon Steel Chemical Co., Ltd. bisphenol S type epoxy resin), Epicron EXA-1515 (Dainippon Chemical Industry Co., Ltd. bisphenol S type epoxy resin), NC-3000 (Nippon Kayaku Co., Ltd. biphenyl aralkyl phenol type epoxy resin), Epototo ZX-1355, Epototo ZX-1711 (Nippon Chemical Co., Ltd. naphthalenediol type epoxy resin), Epototo ESN-155 (Nippon Steel) Β-naphthol aralkyl type epoxy resin manufactured by Chemical Co., Ltd.), Epototo ESN-355, Epototo ESN-375 (manufactured by Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl type epoxy resin), Epototo ESN475V, Epototo ES N-485 (Nippon Steel Chemical Co., Ltd. α-naphthol aralkyl type epoxy resin), EPPN-501H (Nippon Kayaku Co., Ltd. trisphenyl methane type epoxy resin), Sumiepoxy TMH-574 (Sumitomo Chemical Co., Ltd. trisphenyl) An epoxy compound produced from a phenol compound of a polyhydric phenol resin such as a methane type epoxy resin) and an epihalohydrin, Epototo YH-434 (Nippon Steel Chemical Co., Ltd. diaminodiphenylmethane tetraglycidylamine) and an amine compound and an epihalohydrin Epoxy resin produced from JER 630 (Aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epototo FX-289B, Epotot FX-305, TX-0932A (Phosphorus-containing epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) A phosphorus-containing epoxy resin obtained by reacting an epoxy resin such as a phosphorus-containing phenol compound with a modifier such as YSLV-120TE (Bisthioether type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1684 (Nippon Steel) Resorcinol type epoxy resin manufactured by Chemical Co., Ltd.), Denacol EX-201 (resorcinol type epoxy resin manufactured by Nagase ChemteX Corporation), Epiklon HP-7200H (dicyclopentadiene type epoxy resin manufactured by DIC Corporation), urethane-modified epoxy resin, oxazolidone Examples thereof include, but are not limited to, ring-containing epoxy resins, TX-0929, TX-0934 (alkylene glycol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), and the like. These epoxy resins may be used alone or in combination of two or more.

The phosphorus-containing phenol compound (b) has a structure represented by the general formula (2). For example, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ manufactured by Sanko Co., Ltd.), 10- (1,4-dioxynaphthalene ) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinyl hydroquinone (trade name PPQ, manufactured by Hokuko Chemical Co., Ltd.), diphenylphosphenyl-1,4-dioxynaphthalene, 1,4 -Cyclooctylenephosphinyl-1,4-phenyldiol (trade name CPHO-HQ manufactured by Nippon Chemical Industry Co., Ltd.), 1,5-cyclooctylenephosphinyl-1,4-phenyldiol (Nippon Chemical Industry Co., Ltd.) Examples include phosphorus-containing phenolic compounds such as the company name CPHO-HQ), but are limited to these. Not intended to be. These phosphorus-containing phenol compounds can be used in combination of two or more.

（式中Ａは炭素数６から２０のアリーレン基及び／またはトリイル基を表す。式中γは０または１を表し、Ｒ_１及びＲ_２は炭素数１から６の炭化水素基を表し、同一であっても異なっていてもよく、リン原子と共に環状になっていてもよい。）

(In the formula, A represents an arylene group and / or triyl group having 6 to 20 carbon atoms. In the formula, γ represents 0 or 1, R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, and are the same. Or may be different, and may be cyclic with a phosphorus atom.)

  Further, these phosphorus-containing phenol compounds (b) were directly connected to phosphorus atoms such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA manufactured by Sanko Co., Ltd.) and diphenylphosphine. It can be obtained by a reaction between a phosphorus compound having an active hydrogen group and quinones such as 1,4-benzoquinone and 1,4-naphthoquinone. For HCA-HQ, see JP-A-60-126293, for HCA-NQ, JP-A-61-2236787, and for PPQ, zh. Obshch. Khim, 42 (11), pages 2415-2418 (1972) shows a synthesis method.

The phosphorus-containing compounds (B) used in the production of the phosphorus-containing phenol resin of the present invention include quinones such as 1,4-benzoquinone and 1,4-naphthoquinone with respect to 1.0 mol of phosphorus compounds such as HCA and diphenylphosphine. Is preferably reacted in the range of 0.2 mol to 1.0 mol, more preferably in the range of 0.5 mol to 1.0 mol, and still more preferably in the range of 0.8 mol to 1.0 mol. If the amount is less than 0.5 mol, the amount of phosphorus-containing phenol compound (b) produced is reduced, so that the crosslink density of the cured product is lowered and the physical properties may be deteriorated. Moreover, since unreacted quinone will remain | survive when it exceeds 1.0 mol, it is not preferable. Moreover, phosphorus compounds, such as said HCA and diphenylphosphine, can be mix | blended with the said phosphorus containing phenol compound (b) by reacting quinones at less than 1.0 mol.

The phosphorus-free phenol compound (c) is a compound having two or more phenolic hydroxyl groups in one molecule, such as hydroxybenzenes such as catechol, resorcinol, hydroquinone, naphthols, biphenols, trisphenols, bisphenol A. , Bisphenol F, bisphenol S, shounol BRG-555 (Phenol novolac resin, manufactured by Showa Denko KK), cresol novolac resin, alkylphenol novolac resin, aralkylphenol novolac resin, triazine ring-containing phenol novolak resin, biphenyl aralkyl phenol resin, resin top TPM -100 (trishydroxyphenyl methane type novolak resin manufactured by Gunei Chemical Industry Co., Ltd.), aralkyl naphthalene diol resin, etc. Lumpur, etc., and the like, but not limited thereto. Moreover, these phosphorus-free phenol compounds can be used in combination of two or more.

  In the present invention, the reaction of the epoxy resin (a) and the phosphorus-containing compound (B) in the first step reaction process is referred to as a precursor reaction, but the precursor reaction does not necessarily have to be completed. The reaction can be stopped halfway to proceed to the second stage reaction step. The unreacted phosphorus-containing compounds (B) in the first-stage reaction are consumed by the reaction with the epoxy resin (a) in the second-stage reaction process, but may further remain as unreacted components. . The precursor reaction is intended to produce a precursor reactant in an amount that expresses the solvent solubility of the phosphorus-containing phenol resin of the present invention, and the phosphorus-containing compound (B) remaining in the phosphorus-containing phenol resin remains. The content is allowed as long as the solvent solubility is not adversely affected.

In the first stage reaction process when producing the phosphorus-containing phenol resin of the present invention, 0.3 mol of the phenolic hydroxyl group contained in the phosphorus-containing phenol compound (b) is 1 mol of the epoxy group of the epoxy resin (a). To 1.5 mol, preferably 0.5 mol to 1.1 mol, and if the phosphorus-containing phenol compound (b) is less than 0.3 mol, the cured product has insufficient flame retardancy. When the amount exceeds 1.5 mol, the residual amount of the unreacted phosphorus-containing phenol compound (b) increases, and the solvent solubility may be deteriorated. Further, when the molar ratio of the phenolic hydroxyl group is close to 1 mol, the resulting resin has a high molecular weight, which may cause thickening or gelation. In this case, the precursor reaction is not completed and the epoxy resin (a) It is desirable to stop the reaction in a state in which the phosphorus-containing phenol compound (b) is partially reacted and proceed to the second stage reaction.

The phosphorus-containing compounds (B) used in the first-stage reaction step are in the range of 50% to 100% of all the phosphorus-containing compounds (B) used for the production of the phosphorus-containing phenol resin of the present invention. It is preferable to use so that it becomes, and 80% to 100% is more preferable. If the phosphorus-containing compound (B) used in the first reaction step is less than 50%, a large amount of the phosphorus-containing phenol compound (b) remains in the obtained phosphorus-containing phenol resin, resulting in poor solvent solubility. .

In the first stage reaction step, it is preferable to react 30% to 95%, more preferably 35% to 95% of the epoxy group of the epoxy resin (a). If the reaction rate of the epoxy group is outside this range, the resulting resin has a high molecular weight, resulting in gelation, and the residual amount of the phosphorus-containing phenol compound (b) increases, resulting in poor solvent solubility.

The reaction rate of the epoxy group can be calculated by measuring the epoxy equivalent of the reaction product by the method described in JIS K7236 and determining the number of epoxy groups used in the reaction.

The first stage reaction step can be carried out in a solvent-free or solvent-like manner, but when carried out in a solvent, it is preferably carried out in an aprotic solvent, such as propylene glycol monomethyl ether (PGM), propylene glycol. Examples thereof include monomethyl ether acetate (PMA), dioxane, dialkyl ether, glycol ether, 2-butoxyethanol and the like. These reaction solvents may be used alone or in combination of two or more. The amount of these reaction solvents used is preferably 50% or less of the total weight of the reaction product in the first stage reaction step.

The reaction temperature of the first-stage reaction step is preferably 100 ° C. to 200 ° C., more preferably 140 ° C. to 160 ° C., and the reaction proceeds remarkably slowly below 100 ° C., and the epoxy resin partially decomposes above 200 ° C. There is a fear. The reaction time is preferably 1 to 4 hours.

In the first reaction step, a reaction catalyst can be used to promote the reaction. Catalysts that can be used include phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, quaternary phosphonium salts such as n-butyltriphenylphosphonium bromide and ethyltriphenylphosphonium iodide, 2-ethyl- Examples include imidazoles such as 4-methylimidazole and 2-phenylimidazole, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, and tertiary amines such as triethylamine and benzyldimethylamine. The amount of these catalysts used is preferably in the range of 0.01% to 1%, more preferably 0.05% to 0.5%, based on the total amount of the epoxy resin.

In the method for producing a phosphorus-containing phenol resin of the present invention, after the first reaction step of reacting the epoxy resin (a) with the phosphorus-containing compound (B) is performed, phosphorus is not contained in the second reaction step. Although it is a method of obtaining a phosphorus-containing phenol resin by reacting phenolic compounds having a phenol compound (c) as an essential component, the phosphorus-containing phenol compound (b) and phosphorus-free are contained per 1 mol of the epoxy group of the epoxy resin (a). The phenolic hydroxyl group of all phenolic compounds used in the production of the phosphorus-containing phenolic resin of the present invention, totaled by the phenolic compound (c), is 1.5 mol to 4.5 mol, more preferably 1.7 mol to 3.5 mol, It is preferable to use a phosphorus-free phenol compound so that the amount is preferably from 1.9 mol to 2.5 mol. If the amount is less than 1.5 mol, the resulting resin has a high molecular weight, resulting in gelation, poor solvent solubility, or extremely low Tg of the cured product. Moreover, when it exceeds 4.5 mol, the flame retardance of hardened | cured material will become inadequate.

In the second-stage reaction step, the same reaction solvent as in the first-stage reaction step can be used, and two or more types may be used simultaneously. The amount of reaction solvent used is preferably 50% or less of the total weight of the reaction product.

In the second stage reaction step, the reaction can be carried out at the same reaction temperature as in the first stage reaction step. The reaction time may be one hour or longer.

In the second stage reaction step, the same reaction catalyst as in the first stage reaction step can be used. The amount of the catalyst used is preferably in the range of 0.01 to 10% with respect to the weight of the epoxy resin (a), including the amount used in the first stage reaction step.

The resin composition of the present invention contains the above-described phosphorus-containing phenol resin, but may contain other compounds as necessary. For example, in the case of an epoxy resin composition, an epoxy resin, a curing agent other than the phosphorus-containing phenol resin of the present invention, a curing accelerator, a filler and the like can be mentioned.

Examples of the epoxy resin that can be used in the epoxy resin composition include, but are not limited to, the same types as those used for the synthesis of the phosphorus-containing phenol resin of the present invention. These epoxy resins may be used alone or in combination of two or more.

When an epoxy resin is used in the resin composition of the present invention, the phosphorus-containing phenol resin of the present invention acts as a curing agent for the epoxy resin. The resin composition of this invention can use a hardening | curing agent together with the phosphorus containing phenol resin of this invention. For example, a phosphorus-free phenol compound used in the production of the phosphorus-containing phenol resin, hydrazides such as adipic acid dihydrazide and sebacic acid dihydrazide, imidazole compounds and salts thereof, dicyandiamide, aminobenzoic acid esters, diethylenetriamine, Aliphatic amines such as ethylenetetramine, tetraethylenepentamine, metaxylenediamine and isophoronediamine, aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone and diaminoethylbenzene, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride , Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, etc. Mentioned object, etc. is may be used in combination one or more epoxy resin curing agent conventionally known. The amount of the epoxy resin curing agent containing the phosphorus-containing phenol resin of the present invention is preferably in the range of 0.3 mol to 1.5 mol with respect to 1.0 mol of the epoxy group in the epoxy resin used, and 0.4 mol to 1 More preferably, 2 mol. Moreover, when using together the phosphorus containing phenol resin of this invention and another epoxy resin hardening | curing agent, phosphorus containing phenol resin is 20% or more by weight ratio with respect to the total amount with another epoxy resin hardening | curing agent, Preferably it is 30%. As mentioned above, it is preferable to use so that it may become 40% or more more preferably. If the phosphorus-containing phenol resin is less than 20%, the flame retardancy of the cured product tends to be insufficient.

Moreover, when adjusting fluidity | liquidity, a viscosity, etc., it is possible to use a reactive diluent in the range which does not impair the physical property of the resin composition of this invention. The diluent is preferably a reactive diluent, but may be a non-reactive diluent. As reactive diluent, monofunctional such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, bifunctional such as resorcinol glycidyl ether, neopentyl glycol glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol And polyfunctional glycidyl ethers such as polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerythritol polyglycidyl ether. Non-reactive diluents include benzyl alcohol, butyl diglycol, pine oil and the like.

Moreover, it is possible to use a hardening accelerator as needed for the resin composition of this invention. 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 curing accelerators depend on the epoxy resin to be used, the type of epoxy resin curing agent to be used together, the molding method, the curing temperature, and the required characteristics, but preferably in the range of 0.01% to 20% by weight with respect to the epoxy resin, Furthermore, 0.1% to 10% is preferable.

The resin composition of this invention may mix | blend another thermosetting resin and a thermoplastic resin in the range which does not impair a characteristic. For example, phenol resin, acrylic resin, petroleum resin, indene resin, coumarone indene resin, phenoxy resin, polyurethane, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polyethersulfone, polysulfone, polyetheretherketone, polyphenylene sulfide, Examples thereof include polyvinyl formal, but are not limited thereto.

The resin composition of this invention can mix | blend an inorganic filler and an organic filler as needed. Examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon , Carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber and the like. These fillers are preferably 1% to 70% of the total weight of the resin composition.

The resin composition of the present invention further contains a nuclide additive such as a silane coupling agent, an antioxidant, a mold release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment as necessary. Can be blended. These additives are preferably in the range of 0.01% to 20% of the total weight of the resin composition.

The resin composition of the present invention can be molded and cured by the same method as known phenol resin compositions to obtain a cured product. The molding method and the curing method can be the same methods as those of known phenol resin compositions, and the method unique to the resin composition of the present invention is unnecessary.

The cured epoxy resin of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film and the like.

The present invention is a phosphorus-containing phenolic resin having flame retardancy, and is excellent in workability because of its good solubility in various organic solvents, and the cured epoxy resin has adhesiveness and heat resistance reliability. It was found to be useful as a material for electrical parts such as sealing materials, copper-clad laminates, insulating paints, flame retardant paints, and insulation flame retardant adhesives used for electric and electronic parts.

Examples of the present invention are shown below, but the scope of the present invention is not limited to these examples. Unless otherwise specified, “parts” represents parts by weight, and “%” represents% by weight. The analysis method and measurement method are as follows.

Epoxy equivalent: Conforms to JIS K7236.
Nonvolatile content: JIS K7235-1986
Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms to orthophosphoric acid. Metavanadate and molybdate were reacted in a sulfuric acid acidic solution, the absorbance at 420 nm of the resulting phosphobird molybdate complex was measured, and the phosphorus atom content determined by a previously prepared calibration curve was expressed in wt%. The phosphorus content of the laminate was expressed as the content relative to the resin content of the laminate.
Hydroxyl equivalent: 1,4-dioxane as a solvent, acetylation with 1.5 mol / L acetyl chloride, excess acetyl chloride is deactivated with water, 0.5 mol / L potassium hydroxide is added, and potential difference Titration was performed using a titrator.
Residual amount of phosphorus-containing phenol compound (b): The peak area of the corresponding peak was determined using high performance liquid chromatography and converted from a calibration curve prepared in advance. Specifically, a column (Cadenza CD-C18 (150 mm × 4.6 mm) manufactured by Intact Corporation) was provided in the main body (Agilent 1100 series manufactured by Agilent Technologies), and the column temperature was set to 40 ° C. The eluent is mixed with tetrahydrofuran / acetonitrile mixed solvent (1/1 (volume ratio)) at the start of elution so that the volume ratio is 60:40, and at the start of elution 15 minutes it becomes 20:80. Gradient analysis was performed at a flow rate of 0.7 ml / min. The detector used was a UV detector (280 nm). A calibration curve was prepared by the following method. A sample solution is prepared by dissolving 50 mg of a phosphorus-containing phenol compound (b) in 10 ml of tetrahydrofuran, and 0.1 μl, 0.5 μl, and 1.0 μl of the sample solution are injected into the apparatus, and the analysis is performed under the analysis conditions. It was. When the phosphorus-containing phenol compound (b) is HCA-HQ, the peak area of the retention time is 4.9 minutes, and when it is HCA-NQ, the peak area of the retention time is 10.3 minutes, and the phosphorus-containing phenol determined from the injection amount and the sample concentration Three points were plotted with the amount of compound (b) on the vertical axis and the peak area on the horizontal axis, and linearity was obtained.

Glass transition temperature (DSC): Expressed by DSC extrapolated temperature when measured under a temperature rising condition of 10 ° C./min with a differential scanning calorimeter (EXSTAR 6000 DSC6200 manufactured by SII NanoTechnology Inc.) .
Thermal decomposition resistance (Td5%) TGA: Measured with 10 ° C / min temperature rise condition with differential thermal-thermogravimetric simultaneous measurement device (EXSTAR TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.), reduced by 5% Expressed temperature.
Copper foil peel strength and delamination strength: in accordance with JIS C6481.
Flammability: Conforms to UL94 (Underwriters Laboratories Inc. safety certification standard). Five test pieces were tested, and the total time of the flammable combustion duration after the first and second flame contact (two flames each twice for a total of 10 flames) was expressed in seconds.
Solubility in various solvents: A solvent was added to the obtained phosphorus-containing phenol resin solution at room temperature, followed by stirring, and the appearance when the nonvolatile content was 50% and 25% was observed. A transparent solution was indicated as ◯, a slight cloudiness was observed as Δ, and a separation and sedimentation was observed as ×.

Example 1
A four-necked glass separable flask experimental apparatus equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas introduction pipe was added to a bisphenol F type epoxy resin (trade name YDF-170, manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent). 168.9 g / eq.) 84.5 parts was added, and 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ manufactured by Sanko Co., Ltd.) Melting point 256 ° C., phosphorus content 9.6%, hydroxyl group equivalent 162 g / eq.) 121.7 parts and propylene glycol monomethyl ether acetate (PMA) 59 parts. At this time, the functional group ratio of HCA-HQ to YDF-170 was 1.5. Triphenylphosphine was added to this as a catalyst and reacted at 160 ° C. for 2 hours. The epoxy equivalent after completion of the first stage reaction was 4849 g / eq. The reaction rate of the epoxy group was 92%. 28.5 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd., hydroxyl group equivalent: 114 g / eq.) Was added thereto, followed by further reaction at 160 ° C. for 3 hours. After completion of the reaction, the reaction mixture was diluted with propylene glycol monomethyl ether (PGM). The obtained phosphorus-containing phenol resin is light yellow and transparent, has a nonvolatile content of 70%, a phosphorus content in the solid content of 5.0%, and a hydroxyl group equivalent of 469 g / eq. The residual amount of HCA-HQ was 10.2%. Table 1 shows the charging ratio, the first-stage reaction conditions, and the properties of the resin, and Table 5 shows the solubility in various solvents.

Example 2
The first stage reaction was carried out in the same manner as in Example 1 except that 105.5 parts of HCA-HQ of Example 1 and 83 parts of PMA were used. At this time, the functional group ratio of HCA-HQ to YDF-170 was 1.3, and the epoxy equivalent after completion of the first stage reaction was 2943 g / eq. The reaction rate of the epoxy group was 87%. To this was added 141.5 parts of trishydroxyphenylmethane type novolak resin (trade name Resitop TPM-100, hydroxyl group equivalent 97.5 g / eq., Manufactured by Gunei Chemical Industry Co., Ltd.), and the reaction was carried out in the same manner as in Example 1. After completion, it was diluted with PGM. The obtained phosphorus-containing phenol resin is red and transparent, the non-volatile content is 70%, the phosphorus content in the solid content is 3.1%, and the hydroxyl group equivalent is 207 g / eq. The residual amount of HCA-HQ was 10.6%. Table 1 shows the charging ratio, first-stage reaction conditions, and resin properties, and Table 5 shows the solubility in various solvents.

Example 3
In the same experimental apparatus as in Example 1, 9,4.9-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA manufactured by Sanko Co., Ltd., phosphorus content 14.2%) 54.9 parts. And 1,4-naphthoquinone (Made by Kawasaki Chemical Co., Ltd., 3.4% moisture content) 39.4 parts, 120 parts toluene, stirred at 75 ° C. for 30 minutes, and then removed the water in the system at 110 ° C. The reaction was performed for 90 minutes to synthesize HCA-NQ. At this time, the molar ratio of HCA to 1,4-naphthoquinone was 0.98 mol of 1,4-naphthoquinone with respect to 1.00 mol of HCA. Thereafter, toluene was removed by refluxing, and 84.5 parts of YDF-170 and 72 parts of PMA were added. At this time, the functional group ratio of HCA-NQ to YDF-170 was 1.0. Triphenylphosphine was added as a catalyst to this, and the first stage reaction was carried out in the same manner as in Example 1. The epoxy equivalent after completion of the first stage reaction is 604 g / eq. The reaction rate of the epoxy group was 39%. 49.1 parts of bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd., hydroxyl equivalent: 100 g / eq.) Was added thereto, and the reaction was carried out in the same manner as in Example 1, and diluted with PGM after completion of the reaction. The obtained phosphorus-containing phenol resin was dark brown and transparent, had a nonvolatile content of 70%, a phosphorus content in the solid content of 3.4%, and a hydroxyl group equivalent of 458 g / eq. The residual amount of HCA-NQ was 7.0%. Table 1 shows the charging ratio, first-stage reaction conditions, and resin properties, and Table 5 shows the solubility in various solvents.

Example 4
In the same manner as in Example 3, 60.5 parts of HCA, 43.5 parts of 1,4-naphthoquinone, and 140 parts of toluene were charged and reacted in the same manner as in Example 3 to synthesize HCA-NQ. At this time, the molar ratio of HCA to 1,4-naphthoquinone was 0.98 mol of 1,4-naphthoquinone with respect to 1.00 mol of HCA. After removing toluene, 84.5 parts of YDF-170 was added. At this time, the functional group ratio of HCA-NQ to YDF-170 was 1.1. Triphenylphosphine was added as a catalyst to this, and the first stage reaction was carried out in the same manner as in Example 1. The epoxy equivalent after completion of the first stage reaction is 1151 g / eq. The reaction rate of the epoxy group was 66%. 44.6 parts of BPF was added to this and reacted in the same manner as in Example 1, and diluted with PGM after the reaction was completed. The obtained phosphorus-containing phenol resin is dark brown and transparent, has a non-volatile content of 70%, a phosphorus content in the solid content of 3.7%, and a hydroxyl group equivalent of 464 g / eq. The residual amount of HCA-NQ was 5.9%. Table 1 shows the charging ratio, first-stage reaction conditions, and resin properties, and Table 5 shows the solubility in various solvents.

Example 5
In the same manner as in Example 3, 129.7 parts of HCA, 93.1 parts of 1,4-naphthoquinone, and 300 parts of toluene were charged and reacted in the same manner as in Example 3 to synthesize HCA-NQ. At this time, the molar ratio of HCA to 1,4-naphthoquinone was 0.98 mol of 1,4-naphthoquinone with respect to 1.00 mol of HCA. After removing toluene, 84.5 parts of YDF-170 was added. At this time, the functional group ratio of HCA-NQ to YDF-170 was 1.2. Triphenylphosphine was added as a catalyst to this and reacted at 160 ° C. for 3 hours. The epoxy equivalent after completion of the first stage reaction is 2750 g / eq. The reaction rate of the epoxy group was 75%. 40.0 parts of BPF was added thereto and the reaction was carried out in the same manner as in Example 1, and diluted with PGM after the reaction was completed. The obtained phosphorus-containing phenol resin is dark brown and transparent, has a non-volatile content of 70%, a phosphorus content in the solid content of 5.3%, and a hydroxyl group equivalent of 319 g / eq. The residual amount of HCA-NQ was 6.8%. Table 1 shows the charging ratio, first-stage reaction conditions, and resin properties, and Table 5 shows the solubility in various solvents.

Example 6
In the same manner as in Example 3, 86.4 parts of HCA, 31.6 of 1,4-naphthoquinone, and 200 parts of toluene were charged and reacted in the same manner as in Example 3 to synthesize HCA-NQ. At this time, the molar ratio of HCA to 1,4-naphthoquinone was 0.50 mol of 1,4-naphthoquinone with respect to 1.00 mol of HCA. After removing toluene, 88.5 parts of phenol novolac type epoxy resin (trade name YDPN-638, manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 176 g / eq.) Was added. At this time, the functional group ratio of HCA-NQ to YDPN-638 was 0.4. Triphenylphosphine was added as a catalyst to this, and the first stage reaction was carried out in the same manner as in Example 1. The epoxy equivalent after completion of the first stage reaction is 2065 g / eq. The reaction rate of the epoxy group was 40%. To this, 114.3 parts of TPM-100 was added, and the reaction was carried out in the same manner as in Example 1, and diluted with PGM after completion of the reaction. The obtained phosphorus-containing phenol resin was dark brown and transparent, had a nonvolatile content of 70%, a phosphorus content in the solid content of 3.8%, and a hydroxyl group equivalent of 252 g / eq. The residual amount of HCA-NQ was 0.8%. Table 1 shows the charging ratio, first-stage reaction conditions, and resin properties, and Table 5 shows the solubility in various solvents.

Example 7
To the phosphorus-containing phenol resin obtained in Example 1, a phenol novolac type epoxy resin (trade name YDPN-638 manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 176 g / eq.) And a curing accelerator in solid amounts shown in Table 2 The resin composition was obtained by blending. This was dissolved in MEK to obtain a resin varnish. The obtained epoxy resin varnish was impregnated into glass cloth (WEA 116E106S136, Nitto Boseki Co., Ltd., thickness 0.1 mm) and dried in a hot air circulating oven at 150 ° C. for 10 minutes to obtain a prepreg. The obtained 4 prepregs and copper foil (3EC-III, Mitsui Mining & Mining Co., Ltd., 35 μm thick) were stacked and vacuum-pressed at 2 MPa under a temperature condition of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes, 0.5 mm thickness A laminate was obtained. Table 2 shows the blending ratio and the evaluation result of the laminate.

Example 8
In the same manner as in Example 7, epoxy resin curing using the phosphorus-containing phenol resin and p-aminophenol type epoxy resin (trade name jER 630 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 105 g / eq.) Obtained in Example 2 I got a thing. Table 2 shows the blending ratio and the evaluation result of the laminate.

Example 9
In the same manner as in Example 7, a cured epoxy resin was obtained using the phosphorus-containing phenol resin and YDPN-638 obtained in Example 3. Table 2 shows the blending ratio and the evaluation result of the laminate.

Example 10
Similarly to Example 7, a cured epoxy resin was obtained using the phosphorus-containing phenol resin obtained in Example 4 and YDPN-638. Table 2 shows the blending ratio and the evaluation result of the laminate.

Example 11
In the same manner as in Example 7, the phosphorus-containing phenol resin and phenol novolac resin obtained in Example 5 (trade name BRG-555 phenolic hydroxyl group equivalent of 105 g / eq. Manufactured by Showa Denko KK), cresol novolac epoxy resin (new) An epoxy resin cured product was obtained using a product name YDCN-700-7, epoxy equivalent 209 g / eq. Table 2 shows the blending ratio and the evaluation result of the laminate.

Example 12
Similarly to Example 7, a cured epoxy resin was obtained using the phosphorus-containing phenol resin obtained in Example 6 and YDPN-638. Table 2 shows the blending ratio and the evaluation result of the laminate.

Comparative Example 1
YDF-170, HCA-HQ, TPM-100, and PMA having the same blending amount as in Example 2 were charged all at once, triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 5 hours. This was diluted by adding a PGM mixed solvent to a non-volatile content of 70%, but a white solid precipitated. This was dissolved in DMF to determine the residual amount of HCA-NQ, which was 24.4%. Table 3 shows the charging ratio and resin properties, and Table 5 shows the solubility in various solvents.

Comparative Example 2
The first stage reaction was carried out in the same manner as in Example 1 except that 137.9 parts of HCA-HQ of Example 1 and 56 parts of PMA were used. At this time, the functional group ratio of HCA-HQ to YDF-170 was 1.7, and the epoxy equivalent after completion of the first stage reaction was 5421 g / eq. The reaction rate of the epoxy group was 92%. 15.0 parts of BPF was added thereto, and the reaction was performed in the same manner as in Example 1. After completion of the reaction, it was diluted with PGM to a non-volatile content of 70%, but a white solid was precipitated. This was dissolved in DMF, and the residual amount of HCA-NQ was determined to be 14.1%. Table 3 shows the charging ratio and resin properties, and Table 5 shows the solubility in various solvents.

Comparative Example 3
As in Example 2, 43.2 parts of HCA, 15.8 parts of 1,4-naphthoquinone and 100 parts of toluene were charged and reacted in the same manner as in Example 3 to synthesize HCA-NQ. At this time, the molar ratio of HCA to 1,4-naphthoquinone was 0.5 mol of 1,4-naphthoquinone with respect to 1.00 mol of HCA. After removing toluene, 88.5 parts YDPN-638 and 26 parts PMA were added. At this time, the functional group ratio of HCA-NQ to YDPN-638 was 0.2. To this, triphenylphosphine was added as a catalyst, and the reaction was carried out in the same manner as in Example 1. The epoxy equivalent after completion of the first stage reaction was 492 g / eq. The reaction rate of the epoxy group was 20%. To this was added 82.7 parts of TPM-100, and a reaction was carried out in the same manner as in Example 1. After completion of the reaction, it was diluted with PGM. The obtained phosphorus-containing phenol resin is dark brown and transparent, has a non-volatile content of 70%, a phosphorus content in the solid content of 2.7%, and a hydroxyl group equivalent of 355 g / eq. There was no remaining HCA-NQ. Table 3 shows the charging ratio and resin properties, and Table 5 shows the solubility in various solvents.

Comparative Example 4
YDPN-638 and a curing accelerator were blended with the phosphorus-containing phenol resin obtained in Comparative Example 1 in solid amounts shown in Table 5 to obtain a resin composition. This was dissolved in a DMF / MEK mixed solvent to obtain a resin varnish. This was cured in the same manner as in Example 7 to obtain a cured epoxy resin. Table 4 shows the blending ratio and the evaluation result of the laminate.

Comparative Example 5
Similarly to Comparative Example 4, an epoxy resin cured product was obtained using the phosphorus-containing phenol resin and YDPN-638 obtained in Comparative Example 2. Table 4 shows the blending ratio and the evaluation result of the laminate.

Comparative Example 6
Similarly to Example 7, a cured epoxy resin was obtained using the phosphorus-containing phenol resin obtained in Comparative Example 3 and YDPN-638. Table 4 shows the blending ratio and the evaluation result of the laminate.

As shown in Example 1 to Example 6 in Table 1 and Table 5, the book in which the epoxy resin (a), the phosphorus-containing phenol compound (b), and the phosphorus-free phenol compound (c) are reacted in a two-step reaction process. The phosphorus-containing phenol resin obtained by the phosphorus-containing phenol resin production method of the invention is a phosphorus-containing phenol compound (b) as compared with the resin of Comparative Example 1 obtained by the production method in which the reaction is performed in a batch without reacting in two stages. The residual amount of is small, and the solvent solubility is excellent. Moreover, compared with the comparative example 2 made to react so that the phenolic hydroxyl group of a phosphorus containing phenolic compound (b) might be 1.7 mol with respect to 1 mol of epoxy groups of an epoxy resin (a) at the reaction process of the 1st step, It turns out that it is excellent in solvent solubility by making it react by 0.3 mol to 1.5 mol like an Example.

As shown in Example 7 to Example 12 in Table 2, the epoxy resin cured product using the phosphorus-containing phenol resin of the present invention as an epoxy resin curing agent was obtained by the phosphorus-containing phenol obtained in Comparative Example 1 and Comparative Example 2. Compared to the case where a resin is used as a curing agent, it is excellent in heat resistance, heat decomposition resistance, and adhesiveness. Moreover, compared with the case where the phosphorus containing phenol resin obtained by the comparative example 3 is used as a hardening | curing agent, a flame retardance is excellent.

Since the phosphorus-containing phenol resin obtained by the production method of the present invention has good solubility in various organic solvents, it can solve the problem of precipitation when blended with the composition, and is excellent in workability, curability and moldability. Moreover, the resin composition containing the phosphorus-containing phenol resin can exhibit sufficient flame retardancy without using an additive-type flame retardant.

Moreover, when the phosphorus containing phenol resin of this invention is used as hardening | curing agents, such as an epoxy resin, the hardened | cured material excellent in heat-resistant reliability and adhesiveness is obtained.

Claims (8)

Phosphorus-containing compounds (B) containing, as an essential component, a phosphorus-containing phenol compound (b) represented by the general formula (1) in an epoxy resin (a) having an average of 1.8 or more epoxy groups in one molecule; and A phosphorus-containing phenol resin obtained by reacting a bifunctional or higher phosphorus-free phenol compound (c) in a two-step reaction step, wherein the epoxy resin (a) and the phosphorus-containing compound are obtained in the first step reaction step. The manufacturing method of the phosphorus containing phenol resin characterized by including the precursor reaction which makes class (B) react.

(In the formula, A represents an arylene group and / or triyl group having 6 to 20 carbon atoms. In the formula, γ represents 0 or 1, R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, and are the same. Or may be different, and may be cyclic with a phosphorus atom.) The phosphorus-containing phenol according to claim 1, wherein the phenolic hydroxyl group of the phosphorus-containing phenol compound (b) is 0.3 mol to 1.5 mol with respect to 1 mol of the epoxy group of the epoxy resin (a) in the reaction step of the first stage. Manufacturing method of resin. The phosphorus-containing phenol compound (b) used in the first-stage reaction step is 50% to 100% of all the phosphorus-containing phenol compounds (b) used in the production of the phosphorus-containing phenol resin. Item 3. A process for producing a phosphorus-containing phenol resin according to Item 2. The method for producing a phosphorus-containing phenol resin according to any one of claims 1 to 3, wherein a reaction rate of an epoxy group of the epoxy resin (a) in the first-stage reaction step is 30% to 95%. . A phosphorus-containing phenol resin obtained by reacting a bifunctional or higher phosphorus-free phenol compound (c) as a second-stage reaction after completion of the first-stage reaction step, the epoxy group of the epoxy resin (a) 5. The total phenolic hydroxyl group of the phosphorus-containing phenol compound (b) and the phosphorus-free phenol compound (c) is 1.5 mol to 4.5 mol with respect to 1 mol. 5. Of producing a phosphorus-containing phenolic resin. A phosphorus-containing phenol resin obtained by the production method according to any one of claims 1 to 5. A phosphorus-containing phenol resin composition comprising the phosphorus-containing phenol resin according to claim 6. A cured product obtained by curing the phosphorus-containing phenol resin composition according to claim 7.