TW201242985A - Epoxy resin containing phosphorus and nitrogen - Google Patents

Abstract

An objective of this invention is to provide a novel flame retardant epoxy resin. An epoxy resin (A) containing phosphorus and nitrogen within the molecule is obtained by bringing a phosphorus compound represented by the following formula (1) (wherein X represents hydrogen atom or formula (2), n represents 0 or 1, and R1 and R2 represents hydrocarbon group having a carbon number of 1 to 6, and can be the same or different, or form a ring together with the phosphorus atom. In the formula (2), A represents an arylene group and/or a tolyl group having a carbon number of 6 to 10.), a cyanuric acid and an epoxy resin (a) into reaction.

Description

201242985 VI. Description of the Invention: [Technical Field] The present invention relates to an unintelligible flame-retardant epoxy resin containing a phosphorus atom and a nitrogen atom in a molecular structure, and an epoxy resin containing the epoxy resin as an essential component A resin composition and an epoxy resin cured product obtained by curing the cycloolefin resin composition. [Prior Art] The flame retardancy of the epoxy resin has heretofore been carried out by toothing, and is represented by, for example, a brominated epoxy resin using tetrabromobisphenol A as a raw material. However, when a halogenated epoxy resin is used, there is a problem that a highly toxic toothing is generated due to a thermal decomposition reaction when the cured product is burned. On the other hand, in recent years, the (10)-burning technique using a phosphorus compound has been explored, and there has been a proposal to fill in a compound disclosed in Patent Document 4. However, since these compounds are low in solubility in an oxygen resin or a solvent, and are not easily used in an epoxy resin or in a solvent, they are used as disclosed in Patent Document 5 to JP-A. It is reacted with an epoxy resin, and is used as a phosphorus-containing epoxy resin or a phenolic phenol resin to impart solubility to a solvent. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Sho. [Patent Document 5] Japanese Patent Laid-Open No. Hei. No. 2000-309623 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-309623 (Patent Document 7) Japanese Laid-Open Patent Publication No. H-279258 (Patent Document No. 9) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. 2003-040969 [Patent Document 1] [Document] [Non-Patent Document 1] Nishizawa, "Incombustible Polymerization" P60, right column, line 22 to line 27, P166, item 6-8-3, 1992, Dacheng Society [invention] [invented by the invention Problem] In order to further improve the flame retardancy by the phosphorus compound, it is only necessary to increase the phosphorus content, increase the molecular weight, reduce the crosslinking density, or use a high-priced phosphorus-containing compound. On the other hand, the present inventors have focused on the effect of the addition of phosphorus and nitrogen to the flame retardancy described in Non-Patent Document 1 and proposed Japanese Patent Application No. 27-1133108 (WO 2008/143309). . The use of an amine compound as a nitrogen compound can improve the flame retardancy by introducing nitrogen. However, since the epoxy resin reacts with the amine compound, when the amount of introduction is increased, the situation of increasing the purity of the job is the same, the molecular weight is increased, and the viscosity of the resin is increased, and the impregnation property is required. [Means for Solving the Problems] In order to solve the above problems, the present inventors have intensively studied various nitrogen-containing compounds and found that a ring containing ruthenium and nitrogen formed by introducing cyanuric acld into an epoxy resin. The physical properties of the oxyresin are remarkably improved to achieve the present invention. 323320 5 201242985 That is, the present invention relates to a compound (1) containing a phosphorus compound and a ruthenium in the molecule. The phosphorus compound represented by the formula (1), the tri-gas resin (A), which is obtained by the following; Tannic acid reacts with epoxy resin (a) and 0 gas +04^2 (1)

X

Wherein 'X represents a hydrogen atom or a general formula DSD main n is not 〇 or 1; and, in the formula, R丨 and R2 represent a hydrocarbon having a carbon number of 1 to 6 which may be the same or may be the same. For the difference, or may be formed together with the phosphorus atom, the 兵口々兵 shows: 94 money, the above formula 2 is as follows (2)

H0 - A - 0H = medium 'A represents a aryl group and/or a triyl group having a carbon number of 6 to 2G). (2) Although an epoxy resin composition is used to roll the 90% of the functional group of the hardener with respect to the resin of the resin (A). And () a kind of &oxygen; ^ hardened material which is obtained by hardening the epoxy resin composition described in the above (2). [Effects of the Invention] This month is an epoxy resin containing nitrogen and phosphorus by using a specific nitrogen-containing

It is introduced into the epoxy resin structure, and it can be used in an epoxy composition which is difficult to obtain by conventional epoxy-filled epoxy resins, even in the case of impregnation and impregnation. , also V 6 323320 201242985 obtained flame retardancy. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. Specific examples of the phosphorus compound represented by the formula (1) of the present invention include dimethylphosphine, diethylphosphine, diphenylphosphine, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene. - ίο - oxide (HCA 'Sanko Co., Ltd.), dimethyl phosphine oxide, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, 1,4-cyclohexane Phosphine oxide, 1,5-cyclooctylphosphine oxide (CPHO, manufactured by Sakamoto Chemical Co., Ltd.), 10-(2,5-di-phenylphenyl)-i〇H-9-oxygen Hetero-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ), 10-(1,4-dihydroxynaphthyl)-10H-9-oxa-10-disc Phenanthrene-oxide (hereinafter referred to as HCA-NQ), diphenylphosphinyl hydroquinone (manufactured by Behind Chemical Industry Co., Ltd., trade name PPQ), diphenylphosphinyl-L4- Dipyridyl naphthalene, 1,4-extended oxime oxyl oxo-1,4-benzenediol (trade name: CPH0-HQ, manufactured by Nippon Chemical Industry Co., Ltd.), 1,5-cyclooctyloxy Phosphyl 4,4-phenylene glycol (manufactured by Sakamoto Chemical Industry Co., Ltd., trade name Cp ho-hQ) and so on. This cylindrical compound may be used alone or in combination of two or more kinds, but is not limited thereto. In the present invention, cyanuric acid refers to a ratio of s-tripa-2,4,6-triol and s_tripa-2,4,6-trione which represents tautomerism, and the ratio thereof There is no particular limitation. Although the technique of adding dimeric murine acid as a nitrogen-based flame retardant has been disclosed, the melting point is also decomposed at a temperature above 330 Å due to its solvent-free solubility. It is used as an additive due to 323320 7 201242985. There are restrictions on the upper system. After the reaction with the epoxy resin, it is uniform in the epoxy resin composition, so that stable flame retardancy can be obtained. The epoxy resin (a) ' used in the production of the phosphorus-containing epoxy resin (A) of the present invention can be exemplified by Epotohto YD-128 or Epotohto YD-8125 (a bisphenol manufactured by Shinki Steel Chemical Co., Ltd.) Type A epoxy resin),

Epotohto YDF-170, Epotohto YD-8170 (Nippon Steel Chemical Co., Ltd. 'bisphenol F type epoxy resin'), YSLV-80XY (Nippon Steel Chemical Co., Ltd.'s tetramethyl bisphenol F type epoxy Resin), Epotohto YDC-1312 (hydroquinone type epoxy resin), jER ΥΧ4000Η (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), Epotohto YDPN-638 (manufactured by Shinkai Iron Chemical Co., Ltd.) Epoxy resin (phenol novolac), Epotohto YDCN-701 (manufactured by Nippon Steel Chemical Co., Ltd., nonylphenol varnish type epoxy resin), Epotohto ZX-1201C Xinyi Iron Chemical Co., Ltd., bisphenol G-type epoxy resin), TX-0710 (made by Nippon Steel Chemical Co., Ltd., bisphenol S type epoxy resin), NC-3000 (made by Sakamoto Chemical Co., Ltd., biphenyl aralkyl phenol type ring) Oxygen resin), Epotohto ΖΧ-1355, Epotohto ZX-171U, Nippon Steel Chemical Co., Ltd., naphthalene diol type epoxy resin), Epotohto ESN-155 (manufactured by Shinozhao Iron Chemical Co., Ltd., point-naphthol aryl Alkyl epoxy resin), Epotohto ESN-355, ESN-3 75 (Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl epoxy resin), Epotohto ESN475V, ESN-485C, Nippon Steel Chemical Co., Ltd., α-naphthol aralkyl epoxy resin) , ΕΡΡΝ-501Η (made by Nippon Kayaku Co., Ltd., triphenylmethyl 8 323320 201242985 alkyl epoxy resin), YSLV-120TE (made by Nippon Steel Chemical Co., Ltd., disulfide epoxy resin), Epotohto ZX-1684 (manufactured by Nippon Steel Chemical Co., Ltd., resorcinol type epoxy resin), Epicl〇n HP-7200H (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), Epotohto YDG_414 ( Epoxy resin manufactured by Nippon Steel Chemical Co., Ltd., tetrafunctional epoxy resin, etc., which is made of multi-component resin and epihalohydrin; TX-0929, TX-0934, TX-1032C New Day Ethylene oxide manufactured by Iron Chemical Co., Ltd., alkanediol type epoxy resin), etc.; epoxy resin manufactured by an alcohol compound and epihalohydrin; Cellc) Xide 2021 (Daicel Chemical Industry Co., Ltd., aliphatic cyclic gas resin) ), Epotohto YH-434C Nippon Steel Chemical Ring made of amine compound and epidentol, such as diamine diphenyl decane tetraglycidylamine, jER 630 (aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation) Oxygen resin; Epotohto FX-289B, Epotohto FX-305, TX-0940 (manufactured by Nippon Steel Chemical Co., Ltd., phosphorus-containing epoxy resin) and other epoxy tree mites; the above epoxy resin and phosphorus-containing Phosphorus-containing epoxy resin, urethane modified epoxy resin, epoxy resin containing oxazolidone ring, etc., which are modified by phenolic compounds, etc., but are not limited to these rings Oxygen resin. Further, these epoxy resins (a) may be used singly or in combination of two or more. The reaction of the phosphorus compound represented by the formula (1) with cyanuric acid and an epoxy resin is carried out by a known method. _The synthesis sequence can be carried out by reacting the epoxy resin (4) with the tribasic acid, and reacting with the tribasic acid, or reacting the epoxy resin (a) with the phosphorus compound, and then reacting with the trimeric acid. 323320 9 201242985 The epoxy resin (a) can be reacted with the Wei compound and the trimerization stage at the same time. The reaction temperature may be a temperature usually set in the synthetic epoxy resin, and is from 1 〇〇C to 250 ° C' and preferably from 120 至 to 20 (TC. A catalyst may also be used in the reaction to shorten the reaction time or reduce the reaction. The catalyst to be used is not particularly limited, and a catalyst which is usually used in the synthesis of an epoxy resin can be used. For example, a tertiary amine such as a methyl dimethylamine or a tetramethyl gasification material can be used. Phosphates such as ammonium salts, trisuccinylphosphine tris(2 6_-decyloxy)phosphine, ethyltriphenyl (tetra) sulphate salts, 2-methylimidazole, 2-ethyl-4-methyl Various kinds of catalysts such as imidazoles such as imidazole may be used alone or in combination of two or more. However, the catalyst may be used in a plurality of times. The amount of the catalyst is not particularly limited. However, it is preferably 5% or less, preferably 1% or less, and more preferably 0.5% or less with respect to the phosphorus-containing epoxy resin (A). When the amount of the catalyst is excessive, the epoxy resin is used depending on the case. Since the self-polymerization reaction makes the viscosity of the resin high, it is not preferable. An inert solvent can also be used in the reaction. Specifically, hexane or heptane can be used. , Xin Shao, brothel, 曱 曱 烧 戍, 戍 、, 坏 烧 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , diisoamyl ether, nonylphenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl phenyl ether, di- succinyl, sulfhydryl acetyl, tetrahydro, sigma and other ethers, 曱基赛路Su (呢1 cellosolve), methyl cel losolve acetate, ethyl celecoxib, cytosine acetate, ethylene glycol isopropyl scale, diethylene glycol dimethyl ether, Methylethy 1 carbitol, propylene glycol monoterpene, dimethyl ketone, 10 323320 201242985 dimethyl hydrazine, etc., but not limited to these, it is also possible to mix two or more kinds The phosphorus-containing and nitrogen-containing epoxy resin (A) of the present invention is prepared by blending a cured sheet with a curable cerium- and nitrogen-containing epoxy resin composition. A curing agent for epoxy resins, such as a shaft resin or an acid anhydride, an amine, a hydraZide, or an acid poly-polymer. These hardeners may be used alone or in combination. Two or more kinds are used. In the +j1 of these modifiers, a dic_diamide or a hydrazine-based hardener is used as the hardener contained in the curable epoxy resin residue of the present invention. The amount of the hardener used in the epoxy resin composition is preferably from 0.4 to 2.0 equivalents, and is from 0.5 to 2.0 equivalents, based on the epoxy group of the functional group of the epoxy resin. 15 equivalents are preferred, and preferably 5 to 1.0 equivalents. If the hardener is less than 0.4 equivalents or more than 2.0 equivalents based on the equivalent of the epoxy group i, the hardening is incomplete and good hardenability cannot be obtained. Hey. Specific examples of the phenolic refining agent which can be used in the curable epoxy resin composition of the present invention include, for example, Shuang A, Shuang shui, Shuang sui, Shuang shuang K, and S. S, tetramethyl bis-a, tetramethyl biguanide f, tetramethyl bisphenol 3, tetrakisyl bisphenol Z, dihydroxy diphenyl sulfide, 4,4, _ thio bis (3-曱Further, such as catechol, meta-diphenol, methyl resorcinol, hydroquinone, monomethylhydroquinone, di-hydroquinone, etc., may be exemplified. , trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone and other dihydroxybenzenes, dihydroxynaphthalene, dihydroxymethylnaphthalene, trihydroxyl;酴 varnish resin, DC-5 (Nippon Steel Chemical Co., Ltd. has 323320 11 201242985 limited company's 'acid varnish type epoxy resin), naphthol novolac resin and other phenols and / or naphthols and aldehydes Condensate, SN_16〇, SN_395, SN_485 (manufactured by Nippon Steel Chemical Co., Ltd.) and other phenols and/or condensates of naphthols and diphenylene glycol, phenols and/or naphthols and isopropenyl groups a condensate of acetophenone, Type and / or naphthols and dicyclopentadiene reacted was divergent type, and / or associated with class stupid Cai hope based condensing agent of phenolic compound condensates and the like. Examples of the above-mentioned anthracene include, for example, dimethyl, xylene, butyl, pentylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, and the like. Hope, 2-naphthalene and so on. The brewing class can be cited as citric acid, B. NB benzaldehyde, chloral aldehyde, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, pimelic dialdehyde, phthalaldehyde, acrolein. , crotonaldehyde, salicylaldehyde, phthalaldehyde, dihydroxybenzaldehyde and the like. The biphenyl type condensing agent may, for example, be bis(hydroxymethyl)biphenyl, bis(methoxyindenyl)biphenyl, bis(ethoxymethyl)biphenyl or bis(oxymethyl). Other known curing agents which can be used in the curable epoxy resin composition of the present invention include, for example, mercaptotetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, and oleic acid. Trimellitic anhydride, methyl nalic acid 4 acid if, di-ethyltriamine, tri-ethyltetramine, m-phenylenediamine, isophorone diamine (isophorone diamine), diaminodiphenyl fluorene, diamine-based hydrazine, diaminodiphenyl ether, dicyandiamide, as acid and polyamines of 323320 12 201242985 polyacid An amine compound such as a polyamine such as a condensate. Further, 'the hardening agent which hardens by the polymerization which generate|occur|produces an epoxy group, such as a triphenyl phosphine compound, the quaternary salt of the four secrets, and a 2-pyridyl _Ethyl_4_methylimidazole, 2_11-mimi sit 1 ^-ethyl 2-methyl. Rice „ sit and wait for saliva, and such salts with trimellitic acid, iso-cyanuric acid, side salts, benzyl salicylamine, 2'4, 6-three (two Tertiary amines, amines, triterpene chlorinated, etc., four-grade ammonium brines, diazabicyclo compounds, and these compounds with the expectant, age-sensitive varnish, etc. A compound such as an amine or a chelating compound, a succinimide or a sulfonium salt, etc. These curing agents may be used singly or in combination of two or more kinds. Other known ones which can be used in the epoxy resin composition of the present invention The proportion of the conventional epoxy resin hardener is 1 equivalent to that of the epoxy resin, and the functional group of the hardener is 0.5 to 15 equivalents. Further, the polymerization is based on the epoxy, to 1.2 oxygen. And the hardening of the weight of the ^ ^ part of the ring caused by the weight of the ring. The more (four) heterogeneous proportion of 0.2 to 5 tree hair month of the three-disc epoxy resin (A) made of flame retardant epoxy tree moon cake composition t It can also make the machine (4) to adjust the silkiness. As for the organic solvent that can be used, for example, n - ψ # # ^, diol monomethyl ether, etc., propylene, ethyl methyl ethyl Ketones, such as ketones, methanol, ethylamines, benzenes, aromatics, etc., may be formed by mixing one or more of these solvents in an epoxy resin concentration of 3〇 to 8〇323320 201242985 % of the dry circumference is formulated. The composition of the present invention can be formulated as an example of a (four) chemical accelerator, and can be used as a hardening accelerator. Ethyl (tetra), 2-ethyl + methyl light, etc. 2_Methyl)phenol, 1,8-diazabicyclo (5 4 , dimethylaminotriphenylphosphine, tricyclohexylphosphine, triphenylene 1 and other tertiary amines, tin and other metals Compound: Relative two: Benike and other phosphines, Xin 1〇〇! ^ 0 02 to 50 0 ΓΓ ΓΓ ΓΓ ΓΓ 可 可 可 ΓΓ 可 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合 配合Temperature or shortening the hardening time. It can reduce the hardening of the composition of the present invention, and can meet the requirements = lift: hydrogen hydroxide, magnesium talc, talc, garbage talc, titanium oxide, glass powder, oxidized money ball (siiieabau.. (6) η, but it is also possible to use a pigment, etc., for the reason of using an inorganic filler, for example, to improve the impact resistance, and to use hydrogen. When it is a metal hydroxide such as a chemical or a hydroxide lock, it can function as a flame retardant. Even if the phosphorus content is small, it can ensure flame retardancy. In particular, it must be made at a level of 10% or more. However, if the blending amount is more than 150%, the adhesion to the necessary items when used as a laminate is lowered. Further, the resin composition may contain glass fibers, pulp fibers, and A fibrous filler such as a synthetic fiber or a ceramic fiber, or an organic filler such as a fine particle rubber or a thermoplastic elastomer. By curing the phosphorus-containing and nitrogen-containing epoxy resin composition of the present invention, a phosphorus-containing and nitrogen-containing epoxy can be obtained. When the resin is cured, it can be formed into a sheet of a resin 323320 14 201242985, a copper foil with a resin, a prepreg, etc., and after laminating, it is heat-pressed and hardened, thereby obtaining a laminate. Phosphorus-containing epoxy resin hardened. After using the phosphorus-containing and nitrogen-containing epoxy resin of the phosphorus-containing and nitrogen-containing epoxy resin (^) of the present invention, the results of heat-hardening and evaluation of the phosphorus- and nitrogen-containing epoxy resin cured product of the laminate are shown by The phosphorus-containing and nitrogen-containing epoxy resin (A) obtained by reacting a phosphorus compound with cyanuric acid and an epoxy resin (a) is a scaly ring obtained from a conventionally known compound and epoxy resin. When the oxygen resin or the nitrogen compound other than cyanuric acid is used, or the epoxy resin containing no nitrogen introduced into the molecule, the epoxy resin (A) has high flame retardancy. [Examples] The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the scope of the examples. The epoxy equivalents of the epoxy resins synthesized in the examples and the comparative examples were measured in accordance with JIS K 7236. The nitrogen content is calculated from the nitrogen content of the nitrogen compound to the weight ratio of the epoxy resin containing phosphorus and nitrogen. The phosphorus content of the epoxy resin synthesized in the examples and the comparative examples was measured by the following method. That is, after adding 3 m of sulfuric acid to the sample 丨 5 〇 mg, it was heated for 30 minutes. After returning to room temperature, 3.5 ml of nitric acid and 0.5 ml of perchloric acid were added, and the mixture was heated and decomposed until the contents were transparent or yellow. This solution was diluted with water in a 100 ml measuring flask. The sample solution was placed in a 50 ml measuring flask, and 1 drop of phenolphthalein 323320 201242985 (phenolphthalein) indicator was added, followed by addition of 2 m〇1/i ammonia until it became reddish. 2 ml of 50% sulfuric acid was added and water was added. After adding 2.5 g of an aqueous solution of 2. 5 g/l of geminic acid and 5 ml of an aqueous solution of 5 g/l of ammonium molybdate, the volume was adjusted with water. After standing at room temperature for 4 minutes, the measurement was carried out by a spectrophotometer at a wavelength of 440 nm using water as a control. The phosphorus content was determined from the absorbance after a standard curve of the aqueous solution of phosphonium-monohydrogen potassium was used. The glass transition temperature of the hardened material is using a precision instrument (Seik〇

The Exster 6000 manufactured by Instruments Co., Ltd. uses the value of the initial bending point as the glass transition temperature in DSC (Differential Scanning Calorimetry). In TMA (Thermomechanical Analysis) The bending point serves as the glass transfer temperature. The copper foil peeling strength was measured in accordance with JIS C 6481 5.7, and the interlayer adhesive force was measured by peeling between one sheet of the prepreg and the remaining three sheets in accordance with JIS C 6481 5.7. Flame retardancy is measured in accordance with UL (Underwriter Laboratories) specifications. In addition, the remaining time is the total of the remaining time of the test piece. The gel permeation chromatogram was measured by HLC-8220GP.C manufactured by Tosoh Corporation, and the column was TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL manufactured by Tosoh Corporation. The column temperature was 40 ° C, and the solution was subjected to tetrahydrofuran at a flow rate of 1 ml/min and measured by an RI detector. 16 323320 201242985 Fourier Transfer Infrared Spectrometer (FT-IR) was measured using a Flow One wax method manufactured by PerkinElmer and a liquid paraffin (Nujol) method in which a THF solution was coated on a KRS pellet. Example 1 In a four-port separable flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen gas introduction device, 253.11 parts by weight of HCA-HQ and 717.96 parts by weight of Epotohto YDF-170C epoxy group were charged. The equivalent of 169. 8 g / eq) and 30. 73 parts by weight of cyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated and stirred to raise the temperature to 140. Hey. 0. 28 parts by weight of triphenylphosphine (hereinafter, abbreviated as Tpp) as a catalyst was added at 165. (: The reaction was carried out for 4 hours. The epoxy equivalent of the obtained epoxy resin was 392·〇g/e (1, and the nitrogen content was 1.0% by weight%. The filling ratio was 2.4% by weight. The results are shown in Table 1. Example 2 In the same apparatus as in Example 1, after adding 278.20 parts by weight of HCA-NQ, 691.80 parts by weight of Epotohto YDF-170 and 30 parts by weight of cyanuric acid, the temperature was raised. The epoxide equivalent of the obtained cyclic oxime resin is 513. 2g / eq, the nitrogen content is ι · 〇 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 〇 〇 〇 〇 〇 〇 513 513 513 The weight %, the phosphorus content is 2.3 reset %. The results are as shown in the table. Further, for the obtained epoxy resin, the gel permeation chromatography spectrum is shown in Fig. 1, which is shown in Fig. 2 The result of the measurement of the Fourier transform infrared spectrophotometer. Example 3 In the same apparatus as in Example 1, the blend of 175.9 parts by weight of 323320 17 201242985 HCA, 25.73 parts by weight (moisture 3.5% by weight grade, removed Epotohto YD-128, 280. 00 parts by weight of Epotohto YDPN-638, 15 parts by weight of 1,4-naphthalene, 273.37 parts by weight 00 parts by weight of BPA and 30. 00 parts by weight of cyanuric acid 'reacted at 140 ° C for 2 hours. Add 〇. 25 parts by weight of TPP' after reaction at 165 ° C for 4 hours. Add 200 00 parts by weight of Epotohto YDCN-700-7, which was melt-mixed. The obtained epoxy resin had an epoxy equivalent of 465.5 g/eq, a nitrogen content of 1.0% by weight, and a filling ratio of 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 Epotohto YDF-170, 742.36 parts by weight of Epotohto YDPN-638 and 7.68 weight were formulated. After the reaction of the cyanuric acid, the reaction was carried out at 140 ° C for 2 hours. After adding 0.1 part by weight of TPP, the reaction was carried out at 165 ° C for 3 hours. The epoxy equivalent of the obtained epoxy resin was 238. Lg / eq, nitrogen content is 〇. 25 wt%, phosphorus content is 1.70 wt%. The results are as shown in Table 1. Example 5 In the same apparatus as in Example 1, 154.93 parts by weight was charged. HCA and 329.22 parts by weight of benzene were dissolved and dissolved. While paying attention to the exothermic reaction, 109.78 parts by weight (3.5 parts by weight) was added in batches. % Grade, amount) after removal of the 1,4-naphthalenedicarboxylic brewing water. Raising the reaction temperature to carry out dehydration reaction was continued at reflux temperature for 3 hours. After recovering toluene, 727.61 parts by weight of EPPN-501H and 7.68 parts by weight of cyanuric acid were added, and 0.26 part by weight of TPP was added, followed by reaction at 165 ° C for 3 hours. 18 323320 201242985: kg 2 obtained 5: = resin epoxy equivalent weight of 365.7g, eq, nitrogen content of .5 weight K, phosphorus content of 2.20% by weight. The results are summarized as follows: 1 ' For the obtained epoxy resin, the gel permeation stratification is shown in Fig. 3, and the measurement result of the 红外线4 chart material Liye conversion infrared spectrophotometer is shown. Comparative Example 1 The operation of Example 2 was carried out except that the YDF-170 was changed to 748.69 parts by weight, the chloroform@夂_ was not used, and the TPP was changed to 〇25 parts by weight. Phosphorus epoxy resin. 4重量重量%。 The resulting epoxy resin having an epoxy equivalent of 355. lg / eq, a phosphorus content of 2.4% by weight. The results are summarized in Table 1. Comparative Example 2 The same procedure as in Example 2 was carried out except that HCA-NQ was changed to 357.49 parts by weight, EpotohtoYDF-170 was changed to 642.51 parts by weight, cyanuric acid was not used, and TPP was changed to 〇36 parts by weight. Operation to obtain a phosphorus-containing epoxy resin. 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 except that 1,4-naphthalene was brewed; changed to 25.98 parts by weight, Epotohto YD-128 was changed to 257.26 parts by weight, Epotohto YDPN-638 was changed to 280.31 parts by weight, and BPA was changed to 15.02 parts by weight. And replacing the cyanuric acid with 15.02 parts by weight of Ethacure 100 (manufactured by Ethyl Corporation, diaminophenyl), and changing the TPP to 0.26 parts by weight and the Epotohto YDCN-700-7 to 199.85 parts by weight. The same operation as in Example 3 was carried out, 19 323320 201242985 to obtain a phosphorus-containing epoxy resin. 5%重量。 The epoxy group having an epoxy group having a epoxide equivalent weight of 442. Og / eq, a nitrogen content of 0. 20% by weight, a phosphorus content of 2. 50% by weight. The results were summarized as Table 1. Comparative Example 4 except that HCA was changed to 125.50 parts by weight, Epotohto YDF-170 was not used, Epotohto YDPN-638 was changed to 792.40 parts by weight, cyanuric acid was not used, and TPP was changed to 0. The same operation as in Example 4 was carried out except for 21 parts by weight to obtain a phosphorus-containing epoxy resin. The epoxy equivalent of the obtained epoxy resin was 301. lg/eq, and the phosphorus content was 1.80% by weight. The results are summarized in Table 1. Comparative Example 5 The same operation as in Example 5 was carried out except that EPPN-501H was changed to 735.29 parts by weight and no cyanuric acid was used, to obtain a phosphorus-containing epoxy resin.重量重量。 The epoxy group having an epoxy equivalent of 344. 6g / eq, a phosphorus content of 2.20% by weight. The results are summarized in Table 1. Tb Comparative Example 6 In the same apparatus as in Example 1, 163.00 parts by weight of HCA, 817. 00 parts by weight of Epotohto YD-128, and 20,000 parts by weight of acetoguanamine (Tokyo) were charged. Chemical system), 111. 10 parts by weight of thioglycoside, dissolved by heating. The reaction was carried out at 130 ° C for 4 hours to obtain a phosphorus-containing epoxy resin. The obtained epoxy resin has an epoxy equivalent of 433.7 g/eq, a nitrogen content of 1.10% by weight, a phosphorus content of 2.30% by weight, and the results are as shown in Table 1. 〇Comparative Example 7 20 323320 201242985 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 the mixture was heated to dissolve. While paying attention to the reaction exotherm, 56.57 parts by weight of 1,4-naphthalene i was charged in portions. The reaction temperature was raised to carry out dehydration, and the reaction was continued at reflux temperature for 3 hours. After the toluene was recovered, 500.00 parts by weight of Epotohto YD-128, 260. 00 parts by weight of Epotohto YDF-170, and 26.74 parts by weight of benzoguanamine were blended, and the reaction was carried out at 150 ° C for 5 hours. . The obtained epoxy resin had an epoxy equivalent of 463.6 g/eq, a nitrogen content of 1.0% by weight, and a phosphorus content of 2.20% by weight. The results are summarized in Table 1. 21 323320 201242985 Comparative Example 7 260. 00 500. 00 I 26.74 156.69 56. 57 ο 463.4 1.00 j 2.20 Comparative Example 6 817.00 1 20. 00 163.00 ο 433.7 1.10 2.30 Comparative Example 5 735. 29 154.93 1 109.78 1 1 ς〇CO ο 344.6 0 2.20 Comparative Example 4 792· 40 I 1 82.10 125. 50 c5 ο 301.1 0 1.80 Comparative Example 3 257. 26 280.31 199. 85 15. 02 ! 1 1 45. 68 :175.90 1 25.98 i 1 1 0.26 442.0 ! 0.20 2.50 Comparative Example 2 642. 51 i 1 357.49 1 1 ί 0.36 1________ 550.3 0 3.00 Comparative Example 1 748. 69 1 1 1 1 1 251.31 °·25 355.1 0 2.40 Example 5 727.61 7.68 154.93 109. 78 0. 26 365.7 0.25 2. 20 Example 4 130.24 742.36 7.68 119.72 1 1 L-______ CO ο 238.1 0.25 1.70 Example 3 273. 37 280. 00 200. 00 30.00 15.00 175.90 25. 73 0.25 465.5 1.00 2. 50 Example 2 _j 69L80 30.00 i 278.20 , 0.28 513.2 1.00 2.30 Example 1 — ____ 717.96 1- 30.73 251.31 0. 28 392.0 1.00 2.40 YDF-170 YD-128 YDPN-638 YDCN-700-7 EPPN-501H Cyanurethane Ethacure 100 曱 胍Aminophenyl guanamine BPA HCA NQ HCA-NQ HCA-HQ Qu α. Epoxy equivalent (g/e q) Nitrogen content 00 Phosphorus-containing rate (3⁄4) Epoxy resin (^) Phosphorus compound 22 323320 201242985 [Example 6 to Example 10 and Comparative Example 8 to Comparative Example 14] Example 1 was formulated in the formulation of Table 2 to Epoxy resin of Example 5 and Comparative Example 1 to Comparative Example 7, Epotohto YDPN-638, dicyandiamide as a curing agent, or phenol novolac resin manufactured by BRG-557C Showa Denko Co., Ltd., as a curing accelerator After 2E4MZ of the agent, it is dissolved in a solvent such as mercaptoethyl ketone, propylene glycol monoterpene ether or dimethyl decylamine to obtain an epoxy resin composition. The obtained epoxy resin composition was impregnated into a glass cloth of IPC No. 2116 manufactured by Nitto Denko Co., Ltd., and dried at 150 ° C to prepare a prepreg. After laminating a copper foil on the obtained prepreg 4ply, it was heat-hardened at 170 °C or 190 °C for 2 hours at 20 MPa, and then a laminate was obtained as a cured epoxy resin. Table 2 shows the results of the glass transition temperature, copper foil peel strength, interlayer adhesion, and flame retardancy test obtained by TMA and DSC of the laminate.

23 323320 S 201242985 1:3⁄4 Comparative Example 14 100.00 2.27 1.70 116 120 1.63 1.52 Combustion 116 Comparative Example 13 1 100.00 2.42 ig〇89 96 1.20 0.80 Combustion 115 Comparative Example 12 100.00 1 30.47 0.05 170 170 1.30 0.71 Combustion 88 Comparative Example 11 100 00 1 1 σ> co o CO G> 129 135 1.49 0.85 Vl 51 Comparative Example 10 ! 100.00 i ;.2.39 1 0.10 118 123 1.22 0. 85 Vl 46 Comparative Example 9 83. 30 i 1 16. 70 26. 26 0.10 96 109 1.32 1.25 Combustion 86 Comparative Example 8 100.00 2.97 0.50 119 117 2.03 1.93 Combustion 90 ί Example 10 1 1 100.00 28.71 0.02 172 172 1:35 0.72 V-0 30 Example 9 100.00 4.41 0.00 136 143 1.50 0.80 V- 0 1 27 ! Example 8 i 1 100.00 i 1 1 2. 26 1 0.10 113 118 1.41 0.93 V-0 33 i Example 7 80.00 i 20. 00 28.28 0.10 96 110 1.56 1.44 V-0 32 Example 6 ο ο «•Μ 2.68 0.5 120.8 120.4 1.95 2.45 V-0 31 <<< ν—/ ^ ^ ^ i $ ^ Md *Β<>W<Β<<<> *flt w WW tSr w VV www — CO兮ΙΛ 赵 装 装 装 ig? I? iP rtr» VVWW 矽W 'V a CSJCO 兮L〇C〇r - driving DICY BR G-557 2E4MZ -- § . . P ^ o -< -5 ^ ^ 2 g S ^ t Nw/ ww Z ^ S5 ΰ?ί ttsi S 拽昀雄"R Λ mother dyeing cone s $ 讳si: 雄雄犁 s 铧锞 铧锞This « y · · « « _ » · Λ 24 323320 201242985 As shown in Table 1, Table 2, the phosphorus compound represented by the general formula (1) is reacted with cyanuric acid and epoxy resin (a). The epoxy resin (A) containing phosphorus and nitrogen in the molecule is compared with the phosphorus-containing epoxy resin of the comparative example in which the cyanuric acid is not modified, and the flame retardancy is obtained even if the phosphorus content is low. This flame retardancy is more preferable than the use of a nitrogen compound other than cyanuric acid as shown in Comparative Example 3, Comparative Example 6, and Comparative Example 7. Further, as shown in Example 7, Example 10, Comparative Example 6, and Comparative Example 7, even in the case of the hardening system, the epoxy resin (A) containing phosphorus and nitrogen in the molecule of the present invention was used. It shows a high flame retardancy. [Industrial Applicability] The present invention is an epoxy resin (A) containing phosphorus and nitrogen in a molecule obtained by reacting a specific phosphorus compound with cyanuric acid and an epoxy resin, and is available as a flame retardant. An epoxy resin for a circuit board excellent in heat resistance and adhesion. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a gel penetration of an epoxy resin of Example 2. Fig. 2 is an FTIR of the epoxy resin of Example 2. Figure 3 is a gel penetration of the epoxy resin of Example 5. Figure 4 is the FTIR of the epoxy resin of Example 5. [Main component symbol description] None. 25 323320

Claims (1)

201242985 VII. Patent application scope: 1. An epoxy resin (A) containing phosphorus and nitrogen in the molecule, which is a phosphorus compound represented by the following general formula (1), cyanuric acid and an epoxy resin (a) The reaction is obtained; A 1 01+0+R2 (1) X [wherein, X represents a hydrogen atom or a formula 2, and η represents 0 or 1; and, in the formula, 匕 and R 2 represent a carbon number of 1 to 6 a hydrocarbon group, which may be the same or different, or may form a ring together with a phosphorus atom; the above formula 2 is represented by the following formula: HO—A—0H (2) (wherein A represents a carbon number of 6 To 20 aryl and / or tribasic)]. The equivalent of the functional group of the hardener is from 0.4 equivalents to 2.0 equivalents, based on the epoxy group of the epoxy resin (A) as described in the first paragraph of the patent application. Adult. 3. An epoxy resin cured product obtained by hardening an epoxy resin composition as described in claim 2 of the patent application. 323320