JP5591176B2 - Phosphorus and nitrogen containing epoxy resin - Google Patents

Description

  The present invention relates to a halogen-free flame-retardant epoxy resin containing a phosphorus atom and a nitrogen atom in the molecular skeleton, an epoxy resin composition containing the epoxy resin as an essential component, and an epoxy resin obtained by curing the epoxy resin composition It relates to a cured product.

  Conventionally, flame retarding of epoxy resins has been performed by halogenation, as represented by brominated epoxy resins using tetrabromobisphenol A as a raw material. However, when a halogenated epoxy resin is used, there is a problem in that a highly toxic halide is generated due to a thermal decomposition reaction when the cured product is burned. In contrast, in recent years, halogen-free flame retardant technology using phosphorus compounds has been studied, and proposals have been made to apply the phosphorus compounds disclosed in Patent Documents 1 to 4. However, since these phosphorus compounds have low solubility in epoxy resins and solvents and are difficult to use by being mixed in epoxy resins or dissolved in solvents, they are disclosed in Patent Documents 5 to 10. As described above, it is used as a phosphorus-containing epoxy resin and a phosphorus-containing phenol resin by previously reacting with epoxy resins to impart solvent solubility.

Japanese Unexamined Patent Publication No. 47-016436 JP-A-60-126293 JP 61-236787 A JP 05-331179 A Japanese Patent Laid-Open No. 04-11662 JP 2000-309623 A Japanese Patent Laid-Open No. 11-166035 Japanese Patent Laid-Open No. 11-279258 JP 2001-123049 Japanese Patent Laid-Open No. 2003-040969

Nishizawa Hitoshi "Polymer Flame Retardation" P60, right column, lines 22-27, P166, paragraph 6-8-3 1992 Taiseisha

  In order to further improve the flame retardancy, the flame retardancy by the phosphorus compound has only to increase the phosphorus content, the molecular weight increases and the crosslinking density decreases, and an expensive phosphorus-containing compound must be used. There wasn't. In contrast, the present inventors have applied for Japanese Patent Application No. 2007-133108 (WO2008 / 143309), paying attention to the synergistic effect on the flame retardancy of phosphorus and nitrogen described in Non-Patent Document 1. An amine compound was used as the nitrogen compound, and the flame retardancy could be improved by introducing nitrogen. However, since the reaction between the epoxy resin and the amine compound is performed, if the amount of nitrogen introduced is increased, the molecular weight is increased as in the case of increasing the phosphorus content, and the resin viscosity is increased. It was sought after.

（式中Ｘは水素原子又は一般式２を表し、ｎは０または１を表し、そして式中Ｒ₁及びＲ₂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、またはリン原子と共に環状になっていてもよく、前記一般式２は、

（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わす。）により表わされる］
で示されるリン化合物、とシアヌル酸とエポキシ樹脂類（ａ）とを反応して得られるリン及び窒素を分子内に含有するエポキシ樹脂（Ａ）；
（２）上記（１）記載のエポキシ樹脂（Ａ）のエポキシ基１当量に対して硬化剤の官能基を0.4当量〜2.0当量を配合してなるエポキシ樹脂組成物；並びに
（３）上記（２）記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物；
に関する。
である。 In order to solve the above problems, the present inventor has eagerly searched for various nitrogen-containing compounds, and as a result, has found that the physical properties of phosphorus and nitrogen-containing epoxy resin in which cyanuric acid is introduced into the epoxy resin are significantly improved. Completed the invention.
That is, the present invention
(1) The following general formula (1):

(In the formula, X represents a hydrogen atom or general formula 2, n represents 0 or 1, and R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different. Or may be cyclic with a phosphorus atom, and the general formula 2 is

(Wherein A represents an arylene group and / or triyl group having 6 to 20 carbon atoms)]
An epoxy resin (A) containing in its molecule phosphorus and nitrogen obtained by reacting a phosphorus compound represented by formula (2), cyanuric acid and epoxy resins (a);
(2) An epoxy resin composition obtained by blending 0.4 to 2.0 equivalents of a functional group of a curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin (A) described in (1) above; and (3) (2) above (2) ) Cured epoxy resin composition obtained by curing the epoxy resin composition described above;
About.
It is.

  The present invention is an epoxy resin containing nitrogen and phosphorus. By introducing nitrogen into the epoxy resin skeleton using a specific nitrogen-containing compound, workability such as impregnation is not impaired, and a conventional phosphorus-containing epoxy Even in an epoxy resin composition using a phenolic curing agent that is difficult to obtain with a resin, it exhibits high flame retardancy such as flame retardancy.

Gel permeation of the epoxy resin of Example 2 FTIR of the epoxy resin of Example 2 Gel Permeation of Epoxy Resin of Example 5 FTIR of the epoxy resin of Example 5

  Hereinafter, embodiments of the present invention will be described in detail. The phosphorus compound represented by the general formula (1) of the present invention is specifically dimethylphosphine, diethylphosphine, diphenylphosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA Sanko Co., Ltd.), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylenephosphine oxide, 1,5-cyclooctylenephosphine oxide (manufactured by CPHO Nippon Chemical Industry Co., Ltd.), 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 (hereinafter referred to as HCA-NQ), di Phenylphosphinylhydroquinone (trade name PPQ manufactured by Hokuko Chemical Co., Ltd.), diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol (Nippon Chemical Industry) Product name CPHO-HQ), 1,5-cyclooctylenephosphinyl-1,4-phenyldiol (product name CPHO-HQ, manufactured by Nippon Chemical Industry Co., Ltd.), and the like. These phosphorus compounds may be used alone or in combination of two or more, and are not limited thereto.

  In the present invention, cyanuric acid refers to s-triazine-2,4,6-triol and s-triazine-2,4,6-trione which are tautomers, and the ratio is not particularly specified.

  Although a technique in which cyanuric acid is added as a nitrogen-based flame retardant has been disclosed, it has been limited to use as an additive because it has no solvent solubility and decomposes at a melting point of 330 ° C. or higher. By reacting with the epoxy resin, it becomes uniform in the epoxy resin composition, so that stable flame retardancy is obtained.

  The epoxy resins (a) used for producing the phosphorus-containing epoxy resin (A) of the present invention are Epototo YD-128, Epototo YD-8125 (Bisphenol A type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDF-170, Epototo YDF-8170 (Bisphenol F type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YSLV-80XY (Tetramethylbisphenol F type epoxy resin manufactured 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 (Nippon Steel Co., Ltd. phenol novolac type epoxy resin), Epototo YDCN-701 (Nippon Steel Chemical Co., Ltd. Cresol novolak) Type epoxy resin), Epototo ZX-1201 (Bisphenol fluorene type epoxy manufactured by Nippon Steel Chemical Co., Ltd.) Fat), TX-0710 (Bisphenol S type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000 (Biphenylaralkylphenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Epototo ZX-1355, Epotot ZX-1711 (New Naphthalenediol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ESN-155 (beta-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ESN-355, Epototo ESN-375 (Nippon Steel Chemical Co., Ltd.) Dinaphthol aralkyl epoxy resin), Epototo ESN475V, Epototo ESN-485 (Nippon Steel Chemical Co., Ltd. α-naphthol aralkyl epoxy resin), EPPN-501H (Nippon Kayaku Co., Ltd. trisphenylmethane epoxy resin) YSLV-120TE (Bisthioether type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1684 (Nippon Steel Chemical Co., Ltd.) Of resorcinol type epoxy resin made by a formula company), Epicron HP-7200H (dicyclopentadiene type epoxy resin made by DIC Corporation), Epototo YDG-414 (tetrafunctional epoxy resin made by Nippon Steel Chemical Co., Ltd.), etc. Epoxy resins produced from phenolic compounds and epihalohydrins such as epoxy resins, TX-0929, TX-0934, TX-1032 (alkylene glycol type epoxy resins manufactured by Nippon Steel Chemical Co., Ltd.), and epihalohydrins , Celoxide 2021 (aliphatic cyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.), Epototo YH-434, (Diaminodiphenylmethanetetraglycidylamine manufactured by Nippon Steel Chemical Co., Ltd.), jER 630 (Aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation) ) And other amine compounds and epihalohydrins Modified epoxy resins such as epoxy resin, Epototo FX-289B, Epototo FX-305, TX-0940 (Phosphorus-containing epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), the above epoxy resins and phosphorus-containing phenolic compounds, etc. Examples thereof include, but are not limited to, phosphorus-containing epoxy resins, urethane-modified epoxy resins, and oxazolidone ring-containing epoxy resins. These epoxy resins (a) may be used alone or in combination of two or more.

  The reaction of the phosphorus compound represented by the general formula (1), cyanuric acid and the epoxy resin is carried out by a known method. As a synthetic procedure, after reacting the epoxy resins (a) and cyanuric acid, the phosphorus compound may be reacted. After reacting the epoxy resins (a) and the phosphorus compound, cyanuric acid may be reacted. You may react resin (a), a phosphorus compound, and cyanuric acid simultaneously.

  The reaction temperature may be a temperature usually set for the synthesis of an epoxy resin, and is 100 ° C to 250 ° C, preferably 120 ° C to 200 ° C.

  A catalyst may be used for the reaction to shorten the time and reduce the reaction temperature. The catalyst that can be used is not particularly limited, and those usually used for the synthesis of epoxy resins can be used. For example, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium bromide, etc. Various catalysts such as phosphonium salts, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used, and these may be used alone or in combination of two or more. Absent. Further, it may be divided and used in several times.

  Although the amount of catalyst is not particularly limited, it is 5% or less, more preferably 1% or less, still more preferably 0.5% or less with respect to the phosphorus-containing epoxy resin (A). When the amount of the catalyst is large, the epoxy group self-polymerization reaction proceeds in some cases, which is not preferable because the resin viscosity becomes high.

  An inert solvent may be used for the reaction. Specifically, various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methylphenyl Ethers, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, and other ethers, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol , Propylene glycol monomethyl ether, dimethylformamide, dimethyl Although sulfoxide or the like can be used, is not limited thereto, it may be used by mixing 2 or more kinds.

  The phosphorus and nitrogen-containing epoxy resin (A) of the present invention can be made into a curable phosphorus and nitrogen-containing epoxy resin composition by blending a curing agent. As the curing agent, various curing resins for epoxy resins such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters can be used, and only one of these curing agents is used. Or you may use two or more types. Of these, dicyandiamide or a phenolic curing agent is preferable as the curing agent contained in the curable epoxy resin composition of the present invention. In the curable epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.4 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents of the functional group of the curing agent with respect to 1 equivalent of the epoxy group that is a functional group of the epoxy resin. Particularly preferred is 0.5 to 1.0 equivalent. When the curing agent is less than 0.4 equivalent or 1 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  Specific examples of the phenolic curing agent that can be used in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, and tetramethylbisphenol. Bisphenols such as F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4′-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone, monomethyl Dihydroxyben such as hydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone Phenols such as hydroxy, naphthalene, such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene, phenol novolac resin, DC-5 (Cresol novolak resin manufactured by Nippon Steel Chemical Co., Ltd.), naphthol novolak resin // Condensates of naphthols and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical Co., Ltd.) and / or condensates of naphthols and xylylene glycol, Condensates of phenols and / or naphthols with isopropenyl acetophenone, reactants of phenols and / or naphthols and dicyclopentadiene, condensates of phenols and / or naphthols and biphenyl condensing agents, etc. Examples include phenolic compounds

  Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Examples of naphthols include 1-naphthol and 2-naphthol. It is done.

Aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde, sebacin aldehyde And acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like.
Examples of the biphenyl condensing agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, and bis (chloromethyl) biphenyl.

  Other known and commonly used curing agents that can be used in the curable epoxy resin composition of the present invention include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl Acid anhydrides such as nadic acid, polyamidoamine that is a condensate of acids and polyamines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, dicyandiamide, and dimer acid And amine compounds such as

  Furthermore, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4- Imidazoles such as methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole and the like and salts thereof with trimellitic acid, isocyanuric acid, boron, etc., benzyldimethylamine, 2,4,6 Amines such as tris (dimethylaminomethyl) phenol, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds and salts thereof with phenols, phenol novolac resins, etc. boron trifluoride and amines, Complex compounds ether compounds, and aromatic phosphonium or iodonium salts can be exemplified. These curing agents may be used alone or in combination of two or more.

  The blending ratio of other known and commonly used epoxy resin curing agents used in the epoxy resin composition of the present invention is such that the functional group of the curing agent is 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents per equivalent of epoxy group. . In addition, the blending ratio of the curing agent that causes the polymerization of the epoxy group to be cured is 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

  In the flame retardant epoxy resin composition comprising the phosphorus-containing epoxy resin (A) of the present invention, an organic solvent can also be used for viscosity adjustment. Examples of organic solvents that can be used include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, benzene and toluene. Aromatic hydrocarbons etc. are mentioned, What mixed one or more types of these solvents can be mix | blended in the range of 30 to 80 weight% as an epoxy resin density | concentration.

  A hardening accelerator can be used for this invention composition as needed. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5 , 4, 0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and metal compounds such as tin octylate. The curing accelerator is used in an amount of 0.02 to 5.0 parts by weight as required with respect to 100 parts by weight of the epoxy resin component in the epoxy resin composition of the present invention. By using a curing accelerator, the curing temperature can be lowered or the curing time can be shortened.

  A filler can be used for this invention composition as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, and silica balloon, but pigments may be blended. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, when metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant aid and can ensure flame retardancy even if the phosphorus content is small. In particular, if the blending amount is not more than 10%, the impact resistance effect is small. However, if the blending amount exceeds 150%, the adhesiveness, which is a necessary item for use in laminates, is lowered. Moreover, organic fillers, such as fiber fillers, such as glass fiber, a pulp fiber, a synthetic fiber, a ceramic fiber, fine particle rubber, and a thermoplastic elastomer, can also be contained in the said resin composition.

  A phosphorus and nitrogen-containing epoxy resin cured product can be obtained by curing the phosphorus and nitrogen-containing epoxy resin composition of the present invention. At the time of curing, for example, a resin sheet, a copper foil with a resin, a prepreg, and the like are formed and laminated and cured by heating and pressing to obtain a cured phosphorus-containing epoxy resin as a laminated board.

  The phosphorus and nitrogen-containing epoxy resin composition using the phosphorus and nitrogen-containing epoxy resin (A) of the present invention was prepared, and the phosphorus and nitrogen-containing epoxy resin cured product of the laminate were evaluated by heat curing. Phosphorus and nitrogen-containing epoxy resin (A) obtained by reacting an acid with epoxy resins (a) is a phosphorus-containing epoxy resin obtained from a conventionally known phosphorus compound and epoxy resins, or a nitrogen compound other than cyanuric acid. In addition, it showed high flame retardancy compared to a phosphorus-containing epoxy resin in which nitrogen was not introduced into the molecule.

EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these.
Epoxy equivalents of the epoxy resins synthesized in Examples and Comparative Examples were measured according to JIS K 7236.

  The nitrogen content was calculated from the nitrogen content of the nitrogen compound by the weight ratio of phosphorus and nitrogen-containing epoxy resin.

  The phosphorus content of the epoxy resins synthesized in the examples and comparative examples was measured by the following method. That is, 3 ml of sulfuric acid is added to 150 mg of sample and heated for 30 minutes. Return to room temperature, add 3.5 ml of nitric acid and 0.5 ml of perchloric acid and heat decompose until the contents are clear or yellow. This solution is diluted with water in a 100 ml volumetric flask. Add 10 ml of this sample solution to a 50 ml volumetric flask, add 1 drop of phenolphthalein indicator, and add 2 mol / l aqueous ammonia until it becomes slightly red. Add 2 ml of 50% sulfuric acid solution and add water. Add 5 ml of 2.5 g / l ammonium metavanadate aqueous solution and 5 ml of 50 g / 1 ammonium molybdate aqueous solution, and make up to volume with water. After standing at room temperature for 40 minutes, water is measured as a control using a spectrophotometer at a wavelength of 440 nm. A calibration curve is prepared with an aqueous potassium dihydrogen phosphate solution, and the phosphorus content is determined from the absorbance.

  The glass transition temperature of the cured product was Exster 6000 manufactured by Seiko Instruments Inc., DSC used the first inflection point as the glass transition temperature, and TMA used the inflection point as the glass transition temperature.

    Copper foil peel strength was measured according to JIS C 6481 5.7, and interlayer adhesion was measured by peeling between one prepreg and the remaining three sheets according to JIS C 6481 5.7.

    Flame retardancy was measured according to UL (Underwriter Laboratorics) standards. In addition, the after flame time is the sum of the after flame times of five test pieces.

  The gel permeation chromatograph was HSO-8220GPC manufactured by Tosoh Corporation, and the columns were measured by connecting TSKgelG4000HXL, TSKgelG3000HXL, and TSKgelG2000HXL manufactured by Tosoh Corporation in series. The column temperature was 40 ° C., the eluent was tetrahydrofuran, the flow rate was 1 ml / min, and the measurement was performed with an RI detector.

    For the Fourier transform infrared spectrophotometer, Spectum One manufactured by Perkin Elmer Co., Ltd. was used, and measurement was performed by the Nujol method in which a THF solution was applied to KRS pellets.

Example 1.
In a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, HCA-HQ 251.31 parts by weight and Epotot YDF-170 (epoxy equivalent 169.8 g / eq) 717.96 parts by weight, 30.73 parts by weight of cyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged, heated and stirred, and heated to 140 ° C. 0.28 parts by weight of triphenylphosphine (hereinafter TPP) was added as a catalyst and reacted at 165 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin was 392.0 g / eq, the nitrogen content was 1.0% by weight, and the phosphorus content was 2.4% by weight. The results are summarized in Table 1.

Example 2
In the same apparatus as in Example 1, 278.20 parts by weight of HCA-NQ, 691.80 parts by weight of Epototo YDF-170 and 30.00 parts by weight of cyanuric acid were blended and heated. At 130 ° C, 0.28 parts by weight of TPP was added and reacted at 165 ° C for 4 hours. The epoxy equivalent of the obtained epoxy resin was 513.2 g / eq, the nitrogen content was 1.0% by weight, and the phosphorus content was 2.3% by weight. The results are summarized in Table 1. Moreover, about the obtained epoxy resin, the measurement result of a gel permeation chromatograph in FIG. 1 and a Fourier-transform infrared spectrophotometer is shown in FIG.

Example 3
In the same apparatus as in Example 1, 175.90 parts by weight of HCA, 25.73 parts by weight of 1,4-naphthoquinone (a product with a water content of 3.5% by weight, the amount excluding water), Epotot YD-128 273.37 parts by weight, Epotot YDPN-638 280.00 parts by weight , 15.00 parts by weight of BPA and 30.00 parts by weight of cyanuric acid were mixed and reacted at 140 ° C. for 2 hours. Further, 0.25 parts by weight of TPP was added and reacted at 165 ° C. for 4 hours. 200.00 parts by weight of Epototo YDCN-700-7 was added and melt mixed. The epoxy equivalent of the obtained epoxy resin was 465.5 g / eq, the nitrogen content was 1.0% by weight, and the phosphorus content was 2.5% by weight. The results are summarized in Table 1.

Example 4
In the same apparatus as in Example 1, 119.72 parts by weight of HCA, 130.24 parts by weight of Epototo YDF-170, 742.36 parts by weight of Epototo YDPN-638, and 7.68 parts by weight of cyanuric acid were mixed and reacted at 140 ° C. for 2 hours. Further, 0.13 part by weight of TPP was added and reacted at 165 ° C. for 3 hours. The epoxy resin thus obtained had an epoxy equivalent of 238.1 g / eq, a nitrogen content of 0.25% by weight, and a phosphorus content of 1.70% by weight. The results are summarized in Table 1.

Example 5 FIG.
In the same apparatus as in Example 1, 154.93 parts by weight of HCA and 329.22 parts by weight of toluene were charged and dissolved by heating. 109.78 parts by weight of 1,4-naphthoquinone (a product with a water content of 3.5% by weight, the amount excluding water) was charged in portions while paying attention to the reaction exotherm. The reaction temperature was raised and dehydration was performed, and the reaction was continued at reflux temperature for 3 hours. Toluene was recovered, 727.61 parts by weight of EPPN-501H and 7.68 parts by weight of cyanuric acid were added, 0.26 parts by weight of TPP was added, and the reaction was carried out at 165 ° C. for 3 hours. The epoxy equivalent of the obtained epoxy resin was 365.7 g / eq, the nitrogen content was 0.25% by weight, and the phosphorus content was 2.20% by weight. The results are summarized in Table 1. Moreover, about the obtained epoxy resin, the measurement result of a gel permeation chromatograph in FIG. 3 and a Fourier-transform infrared spectrophotometer is shown in FIG.

Comparative Example 1
A phosphorus-containing epoxy resin was obtained in the same manner as in Example 1 except that 748.69 parts by weight of YDF-170 and 0.25 parts by weight of TPP without using cyanuric acid were used. The epoxy equivalent of the obtained epoxy resin was 355.1 g / eq, and the phosphorus content was 2.40% by weight. The results are summarized in Table 1.

Comparative Example 2
A phosphorous-containing epoxy resin was obtained in the same manner as in Example 2 except that 357.49 parts by weight of HCA-NQ, 642.51 parts by weight of Epototo YDF-170, cyanuric acid was not used, and 0.36 parts by weight of TPP was used. The epoxy equivalent of the obtained epoxy resin was 550.3 g / eq, and the phosphorus content was 3.00% by weight. The results are summarized in Table 1.

Comparative Example 3
25.98 parts by weight of 1,4-naphthoquinone, 257.26 parts by weight of Epotate YD-128, 280.31 parts by weight of EDPOT-YDPN-638, 15.02 parts by weight of BPA, 15.02 parts by weight of Ecure 100 (diaminotoluene made by Ethyl Corporation) instead of cyanuric acid, A phosphorus-containing epoxy resin was obtained in the same manner as in Example 3 except that 0.26 parts by weight of TPP and 199.85 parts by weight of Epototo YDCN-700-7 were used. The epoxy equivalent of the obtained epoxy resin was 442.0 g / eq, the nitrogen content was 0.20% by weight, and the phosphorus content was 2.50% by weight. The results are summarized in Table 1.

Comparative Example 4
Phosphorus-containing epoxy using the same procedure as in Example 4 except that 125.50 parts by weight of HCA, Epototo YDF-170 was not used, Epotot YDPN-638 792.40 parts by weight, cyanuric acid was not used, and TPP was 0.21 parts by weight. A resin was obtained. The epoxy equivalent of the obtained epoxy resin was 301.1 g / eq, and the phosphorus content was 1.80% by weight. The results are summarized in Table 1.

Comparative Example 5
A phosphorus-containing epoxy resin was obtained in the same manner as in Example 5 except that 735.29 parts by weight of EPPN-501H and cyanuric acid were not used. The epoxy equivalent of the obtained epoxy resin was 344.6 g / eq, and the phosphorus content was 2.20% by weight. The results are summarized in Table 1.

Comparative Example 6
In the same apparatus as in Example 1, 163.00 parts by weight of HCA, 817.00 parts by weight of Epototo YD-128, 20.00 parts by weight of acetoguanamine (manufactured by Tokyo Chemical Industry), and 111.10 parts by weight of methyl cellosolve were heated and dissolved. Reaction was performed at 130 degreeC for 4 hours, and the phosphorus containing epoxy resin was obtained. The epoxy equivalent of the obtained epoxy resin was 433.7 g / eq, the nitrogen content was 1.10% by weight, and the phosphorus content was 2.30% by weight. The results are summarized in Table 1.

Comparative Example 7
In the same apparatus as in Example 1, 156.69 parts by weight of HCA and 333.00 parts by weight of toluene were charged and dissolved by heating. 56.57 parts by weight of 1,4-naphthoquinone was charged in portions while paying attention to the reaction exotherm. The reaction temperature was raised and dehydration was performed, and the reaction was continued at reflux temperature for 3 hours. Toluene was recovered, 50 to 50 parts by weight of epototo YD-128, 260.00 parts by weight of epototo YDF-170, and 26.74 parts of benzoguanamine were mixed and reacted at 150 ° C. for 5 hours. The epoxy resin thus obtained had an epoxy equivalent of 463.4 g / eq, a nitrogen content of 1.00% by weight, and a phosphorus content of 2.20% by weight. The results are summarized in Table 1.

Examples 6 to 10 and Comparative Examples 8 to 14
Epoxy resins of Examples 1 to 5 and Comparative Examples 1 to 7, Epototo YDPN-638, Dicyandiamide or BRG-557 (Phenol novolac resin manufactured by Showa Denko KK) as a curing agent, and 2E4MZ as a curing accelerator It mix | blended by prescription of Table 2, and melt | dissolved in solvents, such as methyl ethyl ketone, propylene glycol monomethyl ether, and dimethylformamide, and obtained the epoxy resin composition.

  The obtained epoxy resin composition was impregnated into a glass cloth of IPC product number 2116 manufactured by Nittobo Co., Ltd. and dried at 150 ° C. to prepare a prepreg. A copper foil was laminated on the obtained prepreg 4ply and heat-cured at 170 ° C. or 190 ° C. and 20 MPa for 2 hours to obtain a laminate as a cured epoxy resin.

  Table 2 summarizes the results of TMA and DSC glass transition temperatures, copper foil peel strength, interlayer adhesion, and flame retardancy test of the laminate.

  As shown in Table 1 and Table 2, epoxy resin (A) containing phosphorus and nitrogen obtained by reacting the phosphorus compound represented by general formula (1), cyanuric acid and epoxy resins (a) in the molecule. Compared with the phosphorus-containing epoxy resin of the comparative example which does not modify cyanuric acid, flame retardancy is obtained even at a low phosphorus content, and the cyanuric acid shown in comparative example 3, comparative example 6 and comparative example 7 The flame retardancy is much better than when a nitrogen compound other than the above is used. Furthermore, as shown in Example 7, Example 10, Comparative Example 9, and Comparative Example 12, even in a phenol curing system, the use of the epoxy resin (A) containing phosphorus and nitrogen in the molecule according to the present invention is very difficult. Shows flammability.

  The present invention is an epoxy resin (A) containing phosphorus and nitrogen in a molecule obtained by reacting a specific phosphorus compound, cyanuric acid and an epoxy resin, and having excellent flame retardancy, heat resistance and adhesiveness. It can be used as an epoxy resin for circuit boards.

Claims (3)

The following general formula (1):

[Wherein X represents a hydrogen atom or general formula 2, n represents 0 or 1, and R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different. Or may be cyclic with a phosphorus atom, and the general formula 2 is

(Wherein A represents an arylene group and / or triyl group having 6 to 20 carbon atoms)]
An epoxy resin (A) containing, in the molecule, phosphorus and nitrogen obtained by reacting the phosphorus compound represented by the above, cyanuric acid and the epoxy resin (a).   The epoxy resin composition formed by mix | blending 0.4 equivalent-2.0 equivalent of the functional group of a hardening | curing agent with respect to 1 equivalent of epoxy groups of the epoxy resin (A) of Claim 1.   A cured epoxy resin obtained by curing the epoxy resin composition according to claim 2.

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