TWI481635B - Epoxy resin containing phosphorus and nitrogen - Google Patents

Description

Phosphorus and nitrogen containing epoxy resin

The present invention relates to a halogen-free flame-retardant epoxy resin containing a phosphorus atom and a nitrogen atom in a molecular structure, and an epoxy resin composition containing the epoxy resin as an essential component, and hardening the epoxy resin composition A cured epoxy resin.

The flame retardation of the epoxy resin has hitherto been carried out by halogenation, and is represented, for example, by a brominated epoxy resin having tetrabromobisphenol A as a raw material. However, when a halogenated epoxy resin is used, there is a problem that a highly toxic halide is generated due to a thermal decomposition reaction when the cured product is burned. On the other hand, in recent years, a halogen-free flame-retardant technology using a phosphorus compound has been proposed, and a proposal of a phosphorus compound disclosed in Patent Documents 1 to 4 has been proposed. However, since these phosphorus compounds have low solubility with an epoxy resin or a solvent, and are difficult to be used in an epoxy resin or dissolved in a solvent, they are used first, as disclosed in Patent Documents 5 to 10. It is reacted with an epoxy resin, and is used as a phosphorus-containing epoxy resin or a phosphorus-containing phenol resin to impart solubility to a solvent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 47-016436

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 60-126293

[Patent Document 3] Japanese Patent Laid-Open No. 61-236787

[Patent Document 4] Japanese Patent Publication No. 05-331179

[Patent Document 5] Japanese Patent Publication No. 04-11662

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-309623

[Patent Document 7] Japanese Patent Laid-Open No. Hei 11-166035

[Patent Document 8] Japanese Patent Laid-Open No. Hei 11-279258

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2001-123049

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2003-040969

[Non-patent literature]

[Non-Patent Document 1] Nishizawa, "Incombustible Polymerization" P60, right column, line 22 to line 27, P166, item 6-8-3, 1992 Dacheng Society

Regarding the flame retardancy by the phosphorus compound, if the flame retardancy is to be further improved, the phosphorus content can be increased, the molecular weight becomes large, the crosslinking density is lowered, or a high-priced phosphorus-containing compound must be used. 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 the application of Japanese Patent Application No. 2007-133108 (WO 2008/143309). The use of an amine compound as a nitrogen compound improves the flame retardancy by introducing nitrogen. However, since the epoxy resin reacts with the amine compound, when the amount of introduction of nitrogen is to be increased, as in the case of increasing the phosphorus content, the molecular weight becomes large and the viscosity of the resin becomes high, so that the impregnation property and the like are required. .

In order to solve the above problems, the present inventors have intensively studied various nitrogen-containing compounds, and found that the physical properties of the phosphorus-containing and nitrogen-containing epoxy resins formed by introducing cyanuric acid into the epoxy resin are remarkable. Improvements are made to achieve the present invention.

That is, the present invention pertains to the following:

(1) An epoxy resin (A) containing phosphorus and nitrogen in a molecule, which is obtained by reacting a phosphorus compound represented by the following formula (1), cyanuric acid, and an epoxy resin (a); Wherein X represents a hydrogen atom or a formula (2), and n represents 0 or 1; further, in the formula, R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different. Or may form a ring together with a phosphorus atom; the above formula (2) is as shown in the following formula: (wherein, A represents an exoaryl group and/or a triyl group having 6 to 20 carbon atoms)].

(2) an epoxy resin composition which is equivalent to one equivalent of the epoxy group of the epoxy resin (A) according to the above (1), and a functional group of the curing agent of from 0.4 equivalents to 2.0 equivalents;

(3) A cured epoxy resin obtained by curing the epoxy resin composition according to (2) above.

The present invention is an epoxy resin containing nitrogen and phosphorus. By using a specific nitrogen-containing compound to introduce nitrogen into an epoxy resin structure, it is possible to exert a conventional phosphorus-containing ring without impairing workability such as impregnation. The high flame retardancy which is difficult to obtain with an oxyresin makes it difficult to obtain flame retardancy even in an epoxy composition using a phenolic hardener.

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. -10-Oxide (HCA, manufactured by Sanko Co., Ltd.), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclohexane Phosphine oxide, 1,5-cyclooctylphosphine oxide (CPHO, manufactured by Nippon Chemical Industry Co., Ltd.), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10- Phosphenephenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ), 10-(1,4-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10- Oxide (hereinafter referred to as HCA-NQ), diphenylphosphinyl hydroquinone (Beixing Chemical Industry Co., Ltd., trade name PPQ), diphenylphosphinyl-1,4-dihydroxynaphthalene 1,4-cyclooctyloctylphosphinyl-1,4-benzenediol (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ), 1,5-cyclooctylphosphinyl-1, 4-Benzene glycol (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ). These phosphorus compounds may be used singly or in combination of two or more kinds, but are not limited thereto.

In the present invention, cyanuric acid refers to s-three which represents tautomerism. -2,4,6-triol and s-three The ratio of -2,4,6-trione is not particularly limited.

Although a technique of adding cyanuric acid as a nitrogen-based flame retardant has been disclosed, since it has no solvent solubility, the melting point is decomposed at 330 ° C or higher, and thus it is limited in use as an additive. After being reacted 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 may, for example, be Epotohto YD-128 or Epotohto YD-8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol) A type epoxy resin), Epotohto YDF-170, Epotohto YD-8170 (made by Nippon Steel Chemical Co., Ltd., bisphenol F type epoxy resin), YSLV-80XY (made by Nippon Steel Chemical Co., Ltd., SiGe Bisphenol F-type epoxy resin), Epotohto YDC-1312 (hydroquinone epoxy resin), jER YX4000H (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), Epotohto YDPN-638 (Nippon Steel Chemical Co., Ltd. Co., Ltd., phenol novolac type epoxy resin, Epotohto YDCN-701 (manufactured by Nippon Steel Chemical Co., Ltd., cresol novolak type epoxy resin), Epotohto ZX-1201 (Nippon Steel Chemical Co., Ltd., bisphenol oxime type epoxy resin), TX-0710 (made by Nippon Steel Chemical Co., Ltd., bisphenol S type epoxy resin), NC-3000 (made by Nippon Kayaku Co., Ltd., Phenylarylene phenol type epoxy resin), Epotohto ZX-1355, Epotohto ZX-1711 (Nippon Steel Chemical Co., Ltd. , naphthalenediol type epoxy resin), Epotohto ESN-155 (Nippon Steel Chemical Co., Ltd., β-naphthol aralkyl type epoxy resin), Epotohto ESN-355, ESN-375 (Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl type epoxy resin), Epotohto ESN475V, ESN-485 (Nippon Steel Chemical Co., Ltd., α-naphthol aralkyl type epoxy resin), EPPN-501H (made by Nippon Kayaku Co., Ltd., triphenylmethane type epoxy resin), YSLV-120TE (made by Nippon Steel Chemical Co., Ltd., disulfide type epoxy resin), Epotohto ZX-1684 (Nippon Steel Chemical Co., Ltd. Co., Ltd., resorcinol type epoxy resin), Epiclon HP-7200H (dicyclopentadiene type epoxy resin manufactured by DIC Corporation), Epotohto YDG-414 (manufactured by Nippon Steel Chemical Co., Ltd. , tetrafunctional epoxy resin, etc., epoxy resin made of phenolic compound of polyphenol resin and epihalohydrin; TX-0929, TX-0934, TX-1032 (manufactured by Nippon Steel Chemical Co., Ltd., Epoxy resin produced by an alcohol compound and epihalohydrin, such as an alkanediol type epoxy resin; Celloxide 2021 (Daicelization) Industrial Co., Ltd., aliphatic cyclic epoxy resin), Epotohto YH-434 (manufactured by Nippon Steel Chemical Co., Ltd., diaminodiphenylmethanetetraglycidylamine), jER 630 (Mitsubishi Chemical Co., Ltd.) Epoxy resin made from amine compound and epihalohydrin, etc.; Epotohto FX-289B, Epotohto FX-305, TX-0940 (manufactured by Nippon Steel Chemical Co., Ltd., including An epoxy resin such as a phosphorus epoxy resin; a phosphorus-containing epoxy resin obtained by modifying the epoxy resin and a phosphorus-containing phenol compound, an urethane modified epoxy resin, and the like An epoxy resin such as an oxazolidone ring, but is not limited to these epoxy resins. 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 may be carried out by reacting the epoxy resin (a) with cyanuric acid, and then reacting with the phosphorus compound, or reacting the epoxy resin (a) with the phosphorus compound, and then reacting with the cyanide. The acid reaction can also simultaneously react the epoxy resin (a) with the phosphorus compound and cyanuric acid.

The reaction temperature may be a temperature which is usually set at the time of synthesizing the epoxy resin, and is from 100 ° C to 250 ° C, and preferably from 120 ° C to 200 ° C.

A catalyst may also be used in the reaction to shorten the reaction time or lower the reaction temperature. 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 benzyldimethylamine, a quaternary ammonium salt such as tetramethylammonium chloride, or a phosphine such as triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine can be used. Various catalysts such as anthracene salts such as ethyltriphenylphosphonium bromide, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, etc. These catalysts may be used alone or in combination. Two or more types are not limited thereto. In addition, it can also be divided into several uses.

Although the amount of the catalyst is not particularly limited, it is preferably 5% or less, preferably 1% or less, and more preferably 0.5% or less, based on the phosphorus-containing epoxy resin (A). When the amount of the catalyst is excessively large, the epoxy resin is self-polymerized depending on the case, and thus the viscosity of the resin is increased, which is not preferable.

An inert solvent can also be used in the reaction. Specifically, hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, various ethers, diethyl ether, Isopropyl ether, dibutyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl anisole, two Ethers such as alkane, methylfuran, tetrahydrofuran, methyl cellosolve, methyl cellosolve acetate, ethyl cyanidin, cyanidin, ethylene glycol Propyl ether, diethylene glycol dimethyl ether, methylethylcarbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl adenine, etc., but not limited thereto, Two or more types are mixed and used.

The phosphorus-containing and nitrogen-containing epoxy resin (A) of the present invention can be used as a curable phosphorus- and nitrogen-containing epoxy resin composition by blending a curing agent. As the curing agent, various hardeners for epoxy resins which are generally used, such as various phenol resins or acid anhydrides, amines, hydrazides, and acidic polyesters, can be used, and only one of these hardeners can be used. Two or more types can also be used. Among these curing agents, dicyandiamide or a phenolic curing agent is preferably used as the curing agent contained in the curable epoxy resin composition of the present invention. The hardener used in the curable epoxy resin composition of the present invention is preferably used in an amount of from 0.4 to 2.0 equivalents per equivalent of the epoxy group as an epoxy group as an epoxy group. It is preferably 1.5 equivalents, and more preferably 0.5 to 1.0 equivalents. When the amount of the hardener is less than 0.4 equivalents or more than 2.0 equivalents per equivalent of the epoxy group, the hardening is incomplete and the cured properties are not obtained.

Specific examples of the phenolic curing agent which can be used in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, and bisphenol S. , tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl Bisphenols such as -6-t-butylphenol), and examples thereof include catechol, resorcin, methyl resorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, Dihydroxybenzenes such as trimethylhydroquinone, mono-t-butylhydroquinone, di-t-butylhydroquinone, hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene, phenol novolacs Resin, DC-5 (made by Nippon Steel Chemical Co., Ltd., cresol novolak type epoxy resin), phenols such as naphthol novolac resin, and/or condensates of naphthols and aldehydes, SN-160, Hydroxides such as SN-395 and SN-485 (manufactured by Nippon Steel Chemical Co., Ltd.) and/or condensates of naphthols and xylene glycol, phenols and/or naphthols and isopropenylacetophenone Condensates, phenols and/or naphthols and dicyclopentadiene The reaction was, phenols and / or naphthols and biphenyl type condensing agent of phenolic compound condensation products and the like.

Examples of the above phenols include phenol, cresol, xylenol, butyl phenol, amyl phenol, nonyl phenol, butyl methyl phenol, trimethyl phenol, phenyl phenol, etc., and naphthol can be exemplified by 1-naphthalene. Phenol, 2-naphthol, etc.

Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and adipaldehyde. Glyoxal, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, dihydroxybenzaldehyde, and the like.

Examples of the biphenyl condensing agent include bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl, and the like.

Other known curing agents which can be used in the curable epoxy resin composition of the present invention include, for example, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, and partial Anhydride such as trimellitic anhydride, methyl nalic acid, di-ethyltriamine, tri-ethyltetramine, m-phenylenediamine, isophorone diamine , diaminodiphenylmethane, diaminodiphenyl hydrazine, diaminodiphenyl ether, dicyanodiamide, polyamine amine as a condensate of an acid such as a dimer acid and a polyamine Amine compounds and the like.

Further, examples of the curing agent which is cured by polymerization of an epoxy group include a phosphine compound such as triphenylphosphine, a phosphonium salt such as tetraphenylphosphonium bromide, 2-methylimidazole or 2-phenylimidazole. , imidazoles such as 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, and the like, and trimellitic acid, iso-cyanuric acid, Amide salts such as boron, benzyl dimethylamine, amines such as 2,4,6-tris(dimethylaminomethyl)phenol, and quaternary ammonium salts such as trimethylammonium chloride And a diazabicyclo compound, and a compound of such a compound, a salt of a phenol, a phenol novolak resin, a boron trifluoride, an amine, an ether compound, or the like, an aromatic hydrazine or a hydrazine salt. These hardeners may be used singly or in combination of two or more.

The proportion of other well-known conventional epoxy resin hardeners used in the epoxy resin composition of the present invention is from 1 to 1.5 equivalents per equivalent of the epoxy resin, and preferably from 0.5 to 1.5 equivalents. A ratio of 0.8 to 1.2 equivalents. Further, the proportion of the curing agent which causes the polymerization of the epoxy group to be hardened with respect to 100 parts by weight of the epoxy resin is preferably 0.2 to 5 parts by weight.

In the flame retardant epoxy resin composition containing the phosphorus-containing epoxy resin (A) of the present invention, an organic solvent may also be used to adjust the viscosity. Examples of the organic solvent that can be used include decylamines such as N,N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, methanol, ethanol, and the like. An aromatic hydrocarbon such as an alcohol, benzene or toluene may be prepared by mixing one or more of these solvents in an epoxy resin concentration of 30 to 80% by weight.

In the composition of the present invention, a curing accelerator can be used in accordance with the requirements. Examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethyl). a phosphine, a phosphine such as 1,8-diazabicyclo(5,4,0)undecene-7, a phosphine such as triphenylphosphine, tricyclohexylphosphine or triphenylphosphine triphenylborane Metal compounds such as tin octylate. The curing accelerator may be used in an amount of 0.02 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin component in the epoxy resin composition of the present invention. By using a hardening accelerator, the hardening temperature can be lowered or the hardening time can be shortened.

In the composition of the present invention, a filler may be used in accordance with the requirements. Specific examples thereof include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, and silica balloons, but pigments and the like may be blended. The reason why the inorganic filler is generally used is, for example, an improvement in impact resistance. Further, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it functions as a flame-retardant aid, and even if the phosphorus content is small, flame retardancy can be ensured. In particular, it is necessary to make the blending amount above 10%, otherwise the effect of impact resistance is not large. However, if the blending amount exceeds 150%, the adhesion of the necessary items when used as a laminate is lowered. Further, the resin composition may contain a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber, or an organic filler such as a fine particle rubber or a thermoplastic elastomer.

By hardening the phosphorus-containing and nitrogen-containing epoxy resin composition of the present invention, an epoxy resin-containing cured product containing phosphorus and nitrogen can be obtained. When it is hardened, it can be formed into a resin sheet, a copper foil with a resin, a prepreg, etc., and after laminating, it is heat-press-hardened, and the phosphorus-containing epoxy resin cured material which is a laminated board is obtained. .

The result of using the phosphorus-containing and nitrogen-containing epoxy resin of the phosphorus-containing and nitrogen-containing epoxy resin (A) of the present invention and evaluating the phosphorus-containing and nitrogen-containing epoxy resin cured product of the laminate by heat curing showed that 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 phosphorus-containing ring obtained from a conventionally known phosphorus compound and epoxy resin. When the oxygen resin or the nitrogen compound other than cyanuric acid is used, or the phosphorus-containing epoxy resin in which no nitrogen is introduced in 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 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 relative to the weight ratio of the phosphorus and nitrogen containing epoxy resin.

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 ml of sulfuric acid to 150 mg of the sample, 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. 10 ml of this sample solution was placed in a 50 ml measuring flask, and 1 drop of phenolphthalein indicator was added, and 2 mol/l of ammonia water was added until it became pale red. 2 ml of 50% sulfuric acid was added and water was added. After adding 5 ml of an aqueous 2.5 g/l ammonium metavanadate solution and 5 ml of an aqueous 50 g/l ammonium molybdate solution, the solution was made up to volume with water. After leaving at room temperature for 40 minutes, the measurement was carried out by using a spectrophotometer at a wavelength of 440 nm and using water as a control. After a standard curve was prepared using an aqueous solution of potassium dihydrogen phosphate, the amount of phosphorus was determined from the absorbance.

The glass transition temperature of the cured product is Exster 6000 manufactured by Seiko Instruments Co., Ltd., and in DSC (Differential Scanning Calorimetry), the value of the initial bending point is used as the glass transition temperature. In TMA (Thermomechanical Analysis), the bending point is used as the glass transition temperature.

The copper foil peeling strength was measured in accordance with JIS C 6481 5.7, and the interlayer adhesion 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 using HLC-8220GPC manufactured by Tosoh Corporation, and the column was connected in series with 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.

A Fourier Transfer Infrared Spectrometer (FT-IR) was measured using a Flow One method of Perkin Elmer, and a liquid paraffin (Nujol) method in which a THF solution was coated on a KRS pellet.

Example 1

In a four-glass separable flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen gas introduction device, 251.31 parts by weight of HCA-HQ and 717.96 parts by weight of Epotohto YDF-170 (epoxy equivalent of 169.8 g/) were charged. 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 °C. 0.28 parts by weight of triphenylphosphine (hereinafter abbreviated as TPP) as a catalyst was added, and the mixture was reacted at 165 ° C for 4 hours. The epoxy resin obtained had an epoxy equivalent of 392.0 g/eq, a nitrogen content of 1.0% by weight, and a phosphorus content of 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 Epotohto YDF-170 and 30.00 parts by weight of cyanuric acid were blended, and then the temperature was raised. After adding 0.28 parts by weight of TPP at 130 ° C, the reaction was carried out at 165 ° C for 4 hours. The epoxy resin obtained had an epoxy equivalent of 513.2 g/eq, a nitrogen content of 1.0% by weight, and a phosphorus content of 2.3% by weight. The results are summarized in Table 1. Further, with respect to the obtained epoxy resin, the gel permeation chromatography spectrum is shown in Fig. 1, and the measurement result of the Fourier transform infrared spectrophotometer is shown in Fig. 2 .

Example 3

In the same apparatus as in Example 1, 175.90 parts by weight of HCA, 25.73 parts by weight (3.5% by weight of moisture, amount of moisture removed) of 1,4-naphthoquinone, and 273.37 parts by weight of Epotohto YD-128 were formulated. After 280.00 parts by weight of Epotohto YDPN-638, 15.00 parts by weight of BPA and 30.00 parts by weight of cyanuric acid, the mixture was reacted at 140 ° C for 2 hours. After further adding 0.25 parts by weight of TPP, the reaction was carried out at 165 ° C for 4 hours. 200.00 parts by weight of Epotohto YDCN-700-7 was added and melt-mixed. The obtained epoxy resin had an epoxy group equivalent of 465.5 g/eq, a nitrogen content of 1.0% by weight, and a phosphorus content 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 parts by weight of cyanuric acid were mixed and reacted at 140 ° C. 2 hours. After further adding 0.13 parts by weight of TPP, the mixture was reacted at 165 ° C for 3 hours. The epoxy resin 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

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 the mixture was heated to dissolve. While paying attention to the exothermic reaction, a portion of 109.78 parts by weight (3.5% by weight of water and an amount of moisture removed) of 1,4-naphthoquinone was added in portions. The reaction temperature was raised to carry out dehydration, and the 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 parts by weight of TPP was added, followed by reaction at 165 ° C for 3 hours. The epoxy resin obtained had an epoxy equivalent of 365.7 g/eq, a nitrogen content of 0.25 wt%, and a phosphorus content of 2.20 wt%. The results are summarized in Table 1. Further, with respect to the obtained epoxy resin, the gel permeation chromatography spectrum is shown in Fig. 3, and the measurement result of the Fourier transform infrared spectrophotometer is shown in Fig. 4.

Comparative example 1

The same operation as in Example 1 was carried out except that YDF-170 was changed to 748.69 parts by weight, no cyanuric acid was used, and TPP was changed to 0.25 parts by weight to obtain a phosphorus-containing epoxy resin. The epoxy resin 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

The same operation as in Example 2 was carried out except that the HCA-NQ was changed to 357.49 parts by weight, the Epotohto YDF-170 was changed to 642.51 parts by weight, the cyanuric acid was not used, and the TPP was changed to 0.36 parts by weight. Phosphorus containing epoxy resin. The epoxy resin 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

In addition to 1,4-naphthoquinone 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, BPA was changed to 15.02 parts by weight, and Ethacure 100 (manufactured by Ethyl Corporation, II) The same operation as in Example 3 was carried out to obtain a phosphorus-containing ring, except that 15.02 parts by weight of a substituted isocyanic acid was used, and TPP was changed to 0.26 parts by weight, and Epotohto YDCN-700-7 was changed to 199.85 parts by weight. Oxygen resin. The epoxy resin obtained had an epoxy equivalent of 442.0 g/eq, a nitrogen content of 0.20% by weight, and a phosphorus content of 2.50% by weight. Organize the results as shown in 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 0.21 parts by weight. 4 The same operation gave a phosphorus-containing epoxy resin. The epoxy resin obtained had an epoxy equivalent of 301.1 g/eq and a phosphorus content of 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, thereby obtaining a phosphorus-containing epoxy resin. The epoxy resin obtained had an epoxy equivalent of 344.6 g/eq and a phosphorus content of 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 Epotohto YD-128, 20.00 parts by weight of acetoguanamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 111.10 parts by weight of methyl group were charged. Celluloid, heated and dissolved. The reaction was carried out at 130 ° C for 4 hours to obtain a phosphorus-containing epoxy resin. The epoxy resin obtained had an epoxy equivalent of 433.7 g/eq, a nitrogen content of 1.10% by weight, and a phosphorus content of 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 the mixture was heated to dissolve. While paying attention to the exothermic reaction, 56.57 parts by weight of 1,4-naphthoquinone 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 recovering toluene, 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 then the reaction was carried out at 150 ° C for 5 hours. The epoxy resin 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.

[Example 6 to Example 10 and Comparative Example 8 to Comparative Example 14]

The epoxy resin of Example 1 to Example 5 and Comparative Example 1 to Comparative Example 7, Epotohto YDPN-638, dicyanamide or BRG-557 as a hardener (Showa Electric Co., Ltd.) was formulated in the formulation of Table 2. The phenol novolak resin, 2E4MZ as a hardening accelerator, is dissolved in a solvent such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethylformamide 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 the copper foil was laminated 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 an epoxy resin cured product.

Table 2 shows the results of the glass transition temperature, the copper foil peel strength, the interlayer adhesion, and the flame retardancy test obtained by TMA and DSC of the laminate.

As shown in Table 1 and Table 2, an epoxy resin (A) containing phosphorus and nitrogen in a molecule obtained by reacting a phosphorus compound represented by the general formula (1) with cyanuric acid and an epoxy resin (a), When compared with the phosphorus-containing epoxy resin of the comparative example in which the cyanuric acid was not modified, the flame retardancy was obtained even if the phosphorus content was low, and the flame retardancy was compared with Comparative Example 3 and Comparative Example 6. Further, it is more preferable to use a nitrogen compound other than cyanuric acid as shown in Comparative Example 7. Further, as shown in Example 7, Example 10, Comparative Example 6, and Comparative Example 7, even in the phenol curing 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 availability]

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 used as an excellent flame retardancy, heat resistance, and adhesion. Epoxy resin for circuit boards.

Fig. 1 is a gel penetration of the 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.

The first to fourth figures of the present invention are graphs of the relative relationship of data, and are not representative of the constitution of the present invention, and thus are not representative.

Claims (3)

An epoxy resin (A) containing phosphorus and nitrogen in a molecule, which is obtained by reacting a phosphorus compound represented by the following formula (1), cyanuric acid and an epoxy resin (a), wherein The total amount of the phosphide represented by the formula (1), the cyanuric acid and the epoxy resin (a) is 100 parts by weight, and the phosphorus compound represented by the formula (1) is 12 to 27.8 parts by weight. The cyanic acid is 0.7 to 3.1 parts by weight, and the epoxy resin (a) is 69.2 to 87.3 parts by weight; Wherein X represents a hydrogen atom or a formula (2), and n represents 0 or 1; further, in the formula, R ₁ and R ₂ represent a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different. It may also form a cyclic ring together with a phosphorus atom; the above formula (2) is as shown in the following formula: (wherein, A represents an exoaryl group and/or a triyl group having 6 to 20 carbon atoms)]. An epoxy resin composition which is equivalent to 1 equivalent of an epoxy group of the epoxy resin (A) according to the first aspect of the invention, and a functional group of the curing agent of 0.4 to 2.0 equivalents. An epoxy resin cured product obtained by hardening an epoxy resin composition according to item 2 of the patent application.