TW452583B - Phosphorus-containing resin and flame-resistant resin composition consisting - Google Patents

Abstract

This invention provides a flame-resistant resin composition consisting of phosphorus-containing resin, nitrogen-containing resin hardener and hardening enhancer. The flame-resistant resin composition consists of no halogen and exhibits excellent flame-resistance and high heat resistance without adding flame-resistant agent, and makes it useful for the manufacture of adhesion sheets, composite materials, laminates, printed circuit boards, copper foil adhesives and semiconductor sealing materials.

Description

4 5 2 5 8 3 Α7 B7 V. Description of the invention (1) [Field of the invention] The present invention relates to a phosphorus-containing resin and a flame retardant resin composition containing the same. Please read the notes on the back before filling this page) [Background of the invention] Composite materials, especially epoxy resin composite materials, are widely used for their simple processability and high safety. Excellent mechanical and chemical properties are widely used It is used in various fields such as painting, electrical insulation, civil construction materials, adhesives and laminated products. Among them, the laminated board made of epoxy resin has strong bonding force of epoxy resin to reinforcing materials such as glass woven fabrics, and does not cause volatile matter 'small forming shrinkage' during hardening. Therefore, the obtained laminated board has a wide range of use, The advantages of excellent mechanical strength, good electrical insulation, and good chemical resistance greatly improve the reliability of laminated boards, making epoxy laminated boards widely used in electrical oxygen and electronic products. Printed by the Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, in order to respond to the increasingly sophisticated fine lines and high density requirements in printed circuit boards, laminated boards are also required to have more excellent electrical properties, mechanical properties, and heat-resistant processability. For the FR4 laminates that are commonly seen at present, the glass transition temperature after hardening is mostly around 130. For cutting and money hole processing of more than 200C in the printed circuit board manufacturing process, and even welding procedures above 270 ° C, such laminate materials It is possible that cracks or plate bursts may occur during the manufacturing and processing process. Therefore, a variety of laminated board materials that emphasize high thermal stability and high glass transition temperature have been actively developed. In addition, for laminated boards, another important property It is its flame retardant property. In some applications, such as aircraft, automobiles, and mass transit, it poses a direct threat to human health and life. Therefore, the flame-retardant paper size of the printed circuit board is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 1 15875. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Consumption;; Soil printing A7 _____ Β7__ V. Description of the invention (2) Characteristics are absolutely necessary. In order to introduce flame retardant properties into laminated board materials, it is necessary to use certain materials that have flame isolation and reduce combustion properties. For epoxy resin / glass fiber based (or organic fiber) laminated boards, 'using halogen-containing compounds, especially It is a bromine-containing epoxy resin and hardener, and is used in combination with flame retardant additives such as trioxide to meet the stringent requirements for the flame retardant properties of laminated boards (such as UL 94 V-0). In general, epoxy resins need to have a desert content of up to 1 to 2%, and use antimony trioxide or other flame retardants to achieve UL 94 V-0. However, 'the use of high-bromine epoxy resins or antimony trioxide' will undoubtedly pose some danger to humans. First, 'Antimony trioxide has been classified as a carcinogen; on the other hand, in the combustion process, not only will produce corrosive bromine radicals and desertified argon' aromatic compounds with high bromine content will produce highly toxic Brominated furan and dioxin bromide compounds have serious effects on human health and the environment. Therefore, it is urgent to find a new flame retardant material and flame retardant method to improve the pollution and environmental problems caused by the use of brominated epoxy resins in laminated boards. In particular, the use of FR-4 epoxy glass fiber laminates is more demanding. As a new generation of flame retardants with environmental protection concept, dish compounds have been widely studied and applied. For example, red phosphorus or phosphorus organic compounds (such as triphenyl phosphonate, tribenzyl phosphonate, carbonic acid, etc.) are directly used instead of the halogen compound as a flame retardant to improve polymer materials or hardening resins. Ignition characteristics. However, the direct addition of these compounds to the resin does not require a large amount of addition due to the flame retardant efficiency of these compounds. National standards for each paper size (NS) A4 specification (21 × χ% mm) 15875 I ^ -------- ^ --------- (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 45258 3 A7 B7 V. Invention Explanation (3) And because of its low molecular weight, high migration will directly affect the characteristics of the resin substrate: such as electrical properties, uniform strength, etc., causing practical difficulties. In recent years, with the concept of reactive flame retardants and environmental protection and safety considerations, phosphating epoxy resins have been used to replace brominated epoxy resins as formulas for flame retardant laminates, such as US Patent No. 5,376,453. Epoxy phosphates are combined with nitrogen-containing cyclic hardeners to make laminated boards, but in order to make up for the shortcomings of insufficient wall content and difficult to meet the requirements of UL94V-0, a variety of phosphate epoxides have been added; U.S. Patent No. 5458978 uses cyclic epoxy Oxyphosphate is combined with nitrogen-containing epoxy resin and metal compound as a hardener. Its finished glass transition temperature is about 175 ° C, and its flame retardancy reaches UL 94V-0 edge (42 seconds vs. critical value of 50 seconds). U.S. Patent No. 4,973,631 and U.S. Patent No. 5,086156 use trihydrocarbylphosphine chlorides with active argon substituents (such as amine groups) alone or in combination with other amine hardeners for hardening of epoxy resins; however, hardeners are used to introduce phosphorus There are disadvantages of low phosphorus content in the resin, and there is no measurement of actual flame resistance in the two patents. The present invention aims to improve the shortcomings of the current technical order, and aims to improve the basic properties of electrical and mechanical equipment and reduce costs, thus completing the present invention. [Detailed description of the invention] The present invention relates to a phosphorus-containing resin, which is characterized in that it contains a functional group of the following formula (A): ί 111 — 11, equipment ---- 1 --- order-1-11- ---- Egypt (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 3 15875 A7 V. Description of the invention (4

0 = P-01 m (A) The functional group represented by formula (A) in the phosphorus-containing resin of the present invention is obtained by reacting the epoxy group of a cycloaliphatic compound with the following formula ， Winner: 0 = P-0 (B) {Read the notes on the back before filling out this page} Member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives Yinzhi The phosphorous resin of the present invention can be obtained from conventional epoxy resins and 9,1 〇_Dihydro_ 9-oxa-10-phosphoanthracene-ίο-oxide and optionally other reactive gas-containing compounds are prepared by the reaction. The epoxy resin used to make the phosphorus-containing resin of the present invention may be any epoxy resin. Specific examples of the 'resin' include bisphenol glycidyl ether, bisdiol glycidyl ether, stilbenol glycidyl ether, glycidyl ether containing nitrogen ring, glycidyl ether of dihydroxynaphthalene, phenolic polyglycidyl ether, and polyhydroxyl Phenol polyglycidyl ether and the like. Glycidyl ethers of bisphenols include, for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphene AD glycidyl ether, bisphenol S glycidyl ether, tetramethyl bisphenol A glycidyl ether, tetramethyl bis Phenol F glycidyl mystery, tetramethyl bispan AD glycidyl ether, tetramethyl bis-age S glycidyl sheet Paper standards are applicable to Chinese national standards (CNS> A4 specifications (210 mm) 15875 Ministry of Economics and Smart Finance Bureau Printed by a consumer cooperative 45258 3 A7 ______ B7_____ V. Description of the invention (5) Bisphenol glycidyl ether includes, for example, 4,4'-diphenol glycidyl ether, 3,3'-dimethyl-4,44 · dipyridine Glycidyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diphenol glycidyl ether. Resorcinol glycidyl ether includes, for example, resorcinol glycidyl ether, hydroquinone glycidyl ether. Glyceryl ethers, isobutyl hydroquinone glycidyl ethers, and phenolic polyglycidyl ethers include, for example, phenolic polyglycidyl ether 'cresol acetaldehyde polyglycidyl ether, bis fluorene A acetaldehyde polyglycidyl ether. Phenyl poly light The mystery of polyglycidol includes, for example, ginseng (4-transylphenyl) methane polyglycidyl ether, ginseng 4-hydroxyphenyl) ethane polyglycidyl ether, ginseng (4-hydroxyphenyl) propane polyglycidyl ether, ginseng (4-hydroxyphenyl) butane polyglycidyl ether, ginseng (3-methyl-4 -Hydroxyphenyl) methane polyglycidyl ether, ginseng (3,5 · dimethyl-4-hydroxyphenyl) methane polyglycidyl ether, (4 · hydroxybenzyl) ethane polyglycidyl ether, 3,5-Dimethyl-4-hydroxyphenyl) Ethane polyglycidyl ether, dicyclopentene-phenolic polyglycidyl ether. Nitrogen ring-containing glycidyl ethers include, for example, triglycidyl ether of isoamylurate And triglycidyl ethers of cyanurates. Glycidyl bonds of dinaphthylnaphthalenes include, for example, 1,6-dinaphthylnaphthalene diglycidyl ether and 2,6-dihydroxynaphthalene diglycidyl ether. The epoxy The resin can be used singly or as a mixture of two or more kinds. Among them, bisphenol A polyglycidyl ether, phenolic polyglycidyl bond, ginseng (4-transylphenyl) f-polyglycidyl mystery, bicyclic A pentylene-pan chain polyglycidyl ether and a tetrafunctional poly (phenyl-4-hydroxy) ethane polyglycidyl bond, or a mixture thereof. C Please read the precautions on the back before filling in this page) -------- One order · —; --------- The paper size applicable to the Chinese National Standard (CNS) A4 (210 X 297) (%) 5 15875 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (6) Other optional active argon-containing compounds for manufacturing the phosphorous resin of the present invention include amines, bisphenol resins, Resorcinol, polyhydroxyphenol resins and phenols. The amines include, for example, dicyandiamide and diaminodiphenylmethane. Bisphenol resins include, for example, the formula HO-Ph-X-Ph-OH (wherein Ph represents a benzyl group, 乂 = -0: 112- <: ((: 113) 2-,-〇-,-5-,- Compounds represented by (: 〇-,-5〇2-), for example: bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetrafluorene Bisphenol AD'tetramethylbisphenol S, 4,4'diphenol, 3,3'-dimethyl-4,4 £ diphenol, 3,3 ', 5,5' · tetramethyl-4 Diphenols. Hydroquinones include, for example, resorcinol, hydroquinone, and isobutylhydroquinone. Poly (hydroxyphenol) resins include, for example, (4-hydroxyphenyl) methane, (4 -Hydroxyphenyl) ethane, ginseng (4-hydroxybenzyl) propane, ginseng (4-hydroxybenzyl) butan, ginseng (3-methyl-4-hydroxyphenyl) methane, ginseng (3,5- Difyl-4-hydroxybenzyl) methane, 4- (4-hydroxybenzyl) ethane, and (3,5-dimethyl-4-hydroxyphenyl) ethane. Suitable divergent types such as: phenol Formaldehyde condensate 'cresol novolac condensate' Bisphenol A novolac condensate, dicyclopentene-phenol novolac condensate. For the production of the phosphorus-containing resin of the present invention, the proportion of the above components is epoxy equivalent of epoxy resin: Active hydrogen equivalent of compound of formula (B): Active argon equivalent of other active argon-containing compounds = 丨 〇: (5 to 50): (0 to 45), preferably 100: (10 to 50): (0 to 45 The best value is 100: to 40): (0 to 4 5). If the content of the compound of formula (B) is too high, it will cause the viscosity of the resin solution to change. The paper & degree applies to the China Solid Standard (CNS) A4 specification ( 210 > < 297 mm] 15875 ^^ 1 ^^ 1 ^^ 1 nnnn-I ^^ 1 I m. 1 n > ^ i I ^ 1 * t ^ i I ^^ 1 ^^ 1 ^^ 1 ^^ 1 ^^ 1 1 ^ 1 flu I (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4525B 3 A7 ______B7___ V. Description of the invention (7) High, formula (B ) If the content of the compound is too low, the flame retardancy of the hardened product will be deteriorated. If the content of other active hydrogen-containing compounds is too high, the molecular weight of the resin will be too large, and even the phosphorus-containing epoxy resin will be hardened and cannot be used. In the phosphorus-containing resin, in addition to the above components, a catalyst may be further added to facilitate the reaction. The catalyst used includes tertiary amine, tertiary phosphine, quaternary ammonium salt, quaternary phosphorus salt, boron trifluoride complex, lithium Compound Imidazole compounds and their compounds Tertiary amines such as triethylamine, tributylamine, dimethylamine ethanol, dimethylphenylamine, ginseng (N, N · dimethyl-aminomethyl) phenol N, N-dimethyl-aminomethylphenol. Tertiary phosphines such as triphenylphosphine. Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, Ethyl benzyl ammonium vapor, triethyl benzyl ammonium bromide, triethyl benzyl ammonium iodide. Quaternary scale salts such as tetrabutylphosphonium, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium acetate acetate complex, tetraphenylphosphonium, tetraphenylphosphonium bromide , Tetraphenylammonium moth, ethyltriphenylphosphonium gaseous compound, ethyltriphenylphosphonium bromide, ethyltribenzylphosphonium iodide, ethyldiphenylphosphonium acetate complex Triphenylphosphonium acetate phosphonate complex, propyltriphenylphosphonium phosphonate, propyltriphenylphosphonium bromide, propyldiphenylphosphonium moth, butyltriphenylphosphonium carbamide Tribenzyl squamous desert, butyltribenzyl iodide and the like. Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole. (Please read the precautions on the back before filling out this page) Binding ----- The A-size paper is applicable to the National Standard (CNS) A4 (210 X 297 mm) 7 15875 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumption cooperative seal * '' £; A7 B7 V. Description of invention (8) These catalysts can be used alone or in combination of two or more. Preferred catalysts are tertiary amines and imidazole compounds, especially dimethylbenzylamine, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole. The amount of catalyst used is 50 to 50,000 ppm of the total weight of the starting material, preferably 100 to 30, 000 ppm ', more preferably 200 to 10, 000 ppm, and even more It is preferably 500 to 2,000 ppm. If the amount of the hardening accelerator exceeds 50,000 ppm, although the reaction time can be shortened, it has adverse effects on the formation of by-products and subsequent applications such as circuit board laminates, electrical properties, moisture resistance, and water absorption properties. 2. If the amount added is' the reaction rate is too slow and inefficient. The reaction for preparing the phosphorus-containing resin of the present invention can be a melt addition reaction 'in the absence of a solvent' or a reflux reaction in the presence of a solvent. Suitable solvents used include organic aromatics, amidines, protic solvents' ethers, esters, and the like. Suitable organic aromatics are, for example, toluene, xylene. Suitable ketones are, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone. Suitable protic solvents are, for example, N, N-dimethylformamide, N, N-diethylformamide, dimethylmethylenesulfonylamine. Suitable ethers are, for example, ethylene glycol monomethyl ether and propylene glycol monomethyl bond. Suitable esters such as: ethyl acetate, ethyl isopropionate, propylene glycol monomethyl ether ethyl ester = the reaction temperature for preparing the phosphorus-containing resin of the present invention is generally 50 to 350 ° C, preferably 50 to 300 aC, more It is preferably 100 to 250aC, and preferably [00 to 200C. Too high temperature is prone to side reactions and it is difficult to control the reaction speed, and it will promote the deterioration of the resin. The temperature is too low. In addition to the poor efficiency, the paper ’s K degree is suitable for China National Standard (CNS) A 丨 Specifications (2) 〇X) 15875 J. r—-一 —rl II nn I * E- 1 nn! I E.》 5Jt nn-I 1 1 DI (Please read the precautions on the back before filling this page)

Α7 Β7 V. Description of the invention (9) The characteristics of the resin produced are difficult to meet the requirements for high-temperature use. The present invention also relates to a flame-retardant resin composition comprising (a) the moth-containing resin of the present invention, (b) a hardener represented by the following formula (0) and (c) a hardening accelerator. (C) wherein R2 is- [CH2-R3] nH (n is an integer from 0 to 20) or an argon atom; but at least one of R2 is not an argon atom; R1 is NHR2, Cy alkyl, or phenyl; R3 is phenyl, naphthyl, or The base of the formula: A in the formula A represents -0-, -S-, -S02-, -CO-, -CH2-, -C (CH3) 2- or the base of the formula: —ch2——or— Among the groups shown by R3 and A above, the aromatic group may be substituted by one or more substituents selected from the group consisting of hydroxyl, amine, carboxyl, C, and 6 alkyl groups. Hardening accelerators, including tertiary amines, tertiary phosphines, quaternary ammonium salts, phosphonium salts, boron trifluoride complexes, lithium compounds, and compounds and their mixtures < * --- I ---- --- II .... Equipment · --- (_Please read the notes on the back before filling in this page) Order --------- Break the paper printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy China's 0 standard (CNS) A4 specifications (210 X 297 mm) 9 15875 Ministry of Economy Wisdom A7 B7 printed by the production bureau staff consumer cooperatives V. Description of the invention (10) Tertiary amines such as triethylamine, tributylamine, dimethylamine ethanol, dimethylphenylamine, ginseng (N, N, di Methyl-aminomethyl) phenol, N, N-dimethyl-aminomethylphenol tertiary phosphine such as triphenylphosphine. Quaternary ammonium salts such as tetramethylammonium gas, tetramethylammonium bromide, Tetramethyl bond moth, triethylbenzyl ammonium gas, triethylbenzyl ammonium bromide, diethylbenzyl sulfide. Lithium salts such as tetrabutylphosphonium tetrazide Tetramethylene bromide, tetrabutylphosphonium, tetrabutylphosphonium acetate acetate complexes' Tetrabenzyl gaseous compounds, Tetrabenzylphosphonium bromides, Tetraphenylphosphonium iodides, Ethyltribenzyl Hydrazone gas, ethyltriphenylammonium bromide, ethyltribenzyl phosphonium iodide 'ethyldiphenylammonium acetate acetic acid complex, ethyltribenzyl phosphonium ester acid complex, Propyltribenzyl ballast, propyltribenzyl bromide, propyldibenzyl molybdenum'butyltriphenylphosphonium carbide'butyltriphenylphosphonium bromide, butyltribenzyl Β-Miso compounds, such as elixir, such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, etc. These hardening accelerators can be used alone or in combination of two or more. The agents are tertiary amines and imidazole compounds, especially dimethylaniline, 2-methylimidazole, 2-benzylimidazole and 2ethyl · 4-methylimidazole. The amount of hardening accelerator used is epoxy 50 to 5 (K000Ppm, preferably ⑽ to 3,000 ppm, more preferably 2,000 to 10,000 ppm, and more preferably 5,000 to 2,000 ppm by weight of the resin composition ------------ I -------- Order -------- line < Please read the jade meaning on the back of 璜 before filling this page) This paper size applies to China National Standard (CNS) A4 ^ i ^ 21〇x 297

If) 1.5875 3 3 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (u) If the amount exceeds 50,000 ppm, "the male can shorten the reaction time", but for by-products and subsequent applications such as circuit board layers The combination has adverse effects on electrical properties, moisture resistance, and water absorption properties. If the amount is added, the reaction rate is too slow and inefficient. The flame-retardant resin composition of the present invention may contain other phosphorus-free epoxy resins in addition to the phosphorus-containing resin of the present invention. The phosphorus-free epoxy resin may be any epoxy resin, and specific examples thereof include bisphenol glycidyl ether, bisdiol glycidyl ether, hydroquinone glycidyl ether, nitrogen-containing ring glycidyl ether, and dihydroxynaphthalene. Glycidyl ether, formaldehyde polyglycidyl ether and polyhydroxyphenol polyglycidyl ether. Glycidyl ethers of bisphenols include, for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, tetramethyl bisphenol A glycidyl mystery, tetramethyl bis PAN F glycidyl ether, tetramethyl bisphenol AD glycidyl ether, tetramethyl bisphenol S glycidyl bond β bisdiol glycidyl ether includes, for example, 4,4'-diphenol glycidyl ether, 3,3'- Dimethyl-4,4'-diphenol glycidyl hydrazone, 3,3 ', 5,5'-tetramethyl-4,44 · diphenol glycidyl ether. Glycolol glycidyl ether includes, for example, resorcinol glycidyl ether, hydroquinone glycidol, isobutyl hydroquinone glycidyl ether. The novolac polyglycidyl ether includes, for example, novolac polyglycidyl ether, methylphenidin polyglycidyl ether, bisphenol A novolac polyglycidyl ether. Phenyl polyhydroxyphenol polyglycidyl ether includes, for example, ginseng (4-hydroxyphenyl) methane polyglycidyl ether, ginseng (4-hydroxybenzyl) ethane polyglycidyl ether, Ί --------- -· .. Install --------. Order ir- ------- Shun (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS > A4 specifications ( (210x 297 mm) 11 15875 Consumer cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed A7 B7 V. Description of the invention (i2) ginseng (4-hydroxyphenyl) propane polyglycidyl ether, ginseng (4 · jingbenben A) Butyl polyglycidyl ether, ginseng (3-methyl-4-hydroxyphenyl) methane polyglycidyl ether, ginseng (3,5-dimethyl-4-hydroxyphenyl) f-alkane polyglycidyl ether, (4-Hydroxyphenyl) ethane polyglycidyl ether, (3,5_dimethyl_4_ meridylbenzyl) ethane polyglycidyl ether, dicyclopentene-phenolic polyglycidyl mystery ^ Nitrogenous Glycidyl ethers of the ring include, for example, triglycidyl ether of isoamylurate and triglycidyl ether of nitrourate β. The glycidyl mystery of naphthene includes, for example, 1,6-di-glycidyl diglycidyl ether and 2,6-two Hydroxycaecol diglycidyl ether. These cyclic milk waxes can be used in combination with one kind or in combination with two or more kinds. Among them, shuangpan Α polyglycidyl bond, PAN polyglycidyl _, ginseng (4- Hydroxyphenyl) methane polyglycidyl ether, dicyclopentyl-phenolic polyglycidyl ether, and tetrafunctional (phenyl-4 · hydroxy) ethane polyglycidyl or mixtures thereof. Used in combination with phosphorus-free In the case of epoxy resin, the proportion of the phosphorus-containing resin in the present invention accounts for 5 to 100% of the total weight of the epoxy resin, more preferably 20 to 100%, and most preferably 25 to 100%. If the proportion is too low, it may easily cause The flame retardancy and heat resistance are insufficient. In addition to the compound of the formula (C), the flame retardant resin composition of the present invention may also contain other hardeners, such as amines, bisphenol resins, benzoxanthine, and polyhydroxy groups. Phenol resins and phenols, etc. Amines include, for example, dicyandiamine, diaminodiphenylmethane. Bisphenol resins, for example, include formula HCKPh-X-Ph-OH (where Ph indicates the paper size applicable to China's national flag) Standard (CNS) / Vi (210x297 male t) 15875 ------------- installation -------- Order --------- (Please read the unintentional matter on the back before filling out this page) 45258 3 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) Phenyl '乂 = -(: 112-〇 ((: ^ 13) 2-,-〇 _, _ 5-,-(: 0-,-302-) Compounds such as: bisphenol A, bisphenol ρ, bisphenol Ad , Bisphenols, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol eight), tetramethylbisbases, 4,4'diphenol, 3,3'-dimethyl -4,4'diphenol, 3,3 ', 5,5'-tetramethyl-4,4'. Resorcinol includes, for example, resorcinol, hydroquinone, isobutylhydroquinone. Poly (hydroxyphenol) resins include, for example, ginseng (4-hydroxybenzyl) methane, ginseng (4-hydroxyphenyl) ethane, ginseng (4-hydroxyphenyl) propane, ginseng (4-hydroxyphenyl) butane ' Ginseng (3-methyl-4-hydroxyphenyl) methane, ginseng (3,5_dimethyl_4_hydroxyphenyl) methane, (4-hydroxyphenyl) ethane, (3,5_ Dimethyl_4-hydroxyphenyl) ethyl beta is suitable for phenols such as: phenol formaldehyde condensate, yin phenol formaldehyde condensate, bis-A phenol formaldehyde condensate, and dicyclopentene-phenol formaldehyde condensate. In the case of using other hardeners, the ratio of the hardener of the compound of formula (C) is 5 to 100%, more preferably 20 to 100%, and most preferably 25 to 100% of the total weight of the hardener. If the ratio is too low, the flame retardancy and heat resistance are insufficient. In the flame-retardant resin composition of the present invention, the amount of the hardener added depends on the reactive hydrogen equivalent of each hardener and the epoxy equivalent of the epoxy resin, and the appropriate equivalent ratio is 100% of the epoxy equivalent of the epoxy resin. The reactive argon equivalent of the hardener is 20 to 140%. A more suitable equivalent ratio is 100% of the epoxy equivalent of epoxy resin. The reactive argon equivalent of the hardener is 40 to 95%. The equivalent ratio is based on the epoxy equivalent of 100/0, and the reactive hydrogen equivalent of the hardener is 50 to 95%. I .----------, ^ ---------- ^ (. Please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 13 15875 A7 B7 V. Description of the invention (w) When the flame retardant resin composition of the present invention is to be prepared into a varnish, a solvent can be added to adjust the viscosity. Suitable solvents include organic aromatics, ketones, protic solvents, ethers, esters, etc. a Suitable organic aromatics such as toluene and xylene. Suitable ketones are, for example, Propionate, methyl ethyl ketone, methyl isobutyl ketone. Suitable protic solvents are, for example, N, N-dimethylformamide, N, N-diethylamidamine, dimethylasyl. Suitable ethers are, for example, ethylene glycol monomethyl ether and propylene glycol monomethyl ether. Suitable esters are, for example, ethyl acetate, ethyl isopropylate, propylene glycol monomethyl ether ethyl ester. Viscosity is usually adjusted to the range of 20 to 5 00cps / 2 5 ° C. Depending on the end use, the epoxy resin composition of the present invention can also be added with general additives or modifiers, such as heat stabilizers, light stabilizers, ultraviolet light absorbers, and plasticizers. Β The flame-retardant resin composition of the present invention A laminate of steel foil, fiber support, and flame retardant resin composition of the present invention can be made by a method known in the general industry. The flame retardant resin composition of the present invention is used to prepare a varnish. Impregnated fiber substrates such as organic or inorganic fiber substrates such as glass fibers, metal weaves, carbon fibers, aramide fibers, boron, and cellulose are impregnated with fibers The base chair is heated and dried 'to obtain a dry prepreg. The pre-impregnated body can be further formed into a composite material laminated board, or it can be used alone as an adhesive layer for other sepals, or one or more can be combined, and copper foil can be placed on the upper side or the upper and lower sides. Heating the prepreg or its combination table under pressure-the scale of the scale is applicable to the national standard (CNS) Ai specifications (210 κ 297 mm) (please read the back side of the * 1ί entry and fill in this page > I ---- if --------- MC of the Intellectual Property Bureau of the Ministry of Economic Affairs ΗPrinted by the Consumer Cooperative 15S75 14 A7 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to find B7 V. Description of the invention (15 ) The composite board materials obtained have exceeded the current product standards in terms of dimensional stability, chemical resistance, corrosion resistance, moisture absorption and electrical properties, and are suitable for use in electronics, space, transportation, etc. Electrical products, such as used in the manufacture of printed circuit boards and multilayer circuit boards, etc. The flame-retardant resin composition of the present invention can also be prepared into a varnish, coated on copper and cured, and then heated and dried to obtain dried copper pigs. Adhesive (RCC, Resin Coated Copper) »this Foil adhesives can be stored for several months at room temperature 'with good storage stability. The RCC can be further formed into composite laminates' or used alone as an adhesive layer for other films' or a Or multiple combinations' on the upper side or on the upper and lower sides of the layer-by-layer layer-by-layer layering (build-up) one by one, the resulting laminate composite material has dimensional and chemical resistance, chemical resistance, corrosion resistance, absorption Both fishing and electrical properties exceed the current product standards, and are suitable for manufacturing multilayer printed circuit boards used in electronics, space, transportation, etc. The suitable hardening reaction temperature of the flame-retardant resin composition of the present invention is 20 to 350 ° C. , Preferably from 50 to 300 t; more preferably from 100 to 25 0 t, and still more preferably from 120 to 220 ° C ^ If the temperature is too high, side reactions are easy to occur and it is difficult to control the reaction speed, and it may promote the speed of resin degradation Faster temperature; low temperature, in addition to poor efficiency, the resulting resin characteristics are difficult to meet the needs of high temperature use. The flame retardant resin composition according to the present invention does not need to add other processing aids and flame retardant additives, The flame retardancy and heat resistance properties of cyclopentadiene resin can be improved at the same time. The present invention will be further illustrated by the following synthesis examples and examples, but the China Solid State Standard (CNS) A4 specification (210 X 297 cm) will not be applied due to the paper size. 7 15875 (Please read the general Italian matter on the back before filling out this page) Loading ------- f -------- I--Complete 15 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5 2. Description of the invention (M) This limits the scope of the present invention. The components used in the synthesis examples and examples are detailed as follows: Epoxy resin 1 represents the cresol-aldehyde condensation produced by Changchun Artificial Resin Factory and sold under the trade name CNE200ELB. Polyglycidyl ether, the epoxy equivalent of 200 to 220 g / eq 'hydrolyzable gas is 700 ppm or less (ASTM method). Ring Resin 2 represents the phenolic polyglycidyl ether produced by Changchun Artificial Resin Factory and sold under the trade name PNE177. Its epoxy equivalent is between 170 and 190 g / eq. The hydrolyzable gas is below 1000 ppm (ASTM law). Epoxy resin 3 represents the diglycidyl ether of bisphenol A produced by Changchun Artificial Resin Factory and sold under the trade name BE 1 8 8EL. Its epoxy equivalent is between 185 and 195 g / eq, and the hydrolyzable gas is below 200 ppm. The viscosity Between 11000 and 15000cps / 25eC. Epoxy resin 4 stands for Changchun Man-made Resin Factory, trade name BE501, and its epoxy equivalent is between 490 and 510 g / eq °. Gas Resin 5 stands for Changchun Man-made Resin Factory, Tetrabromide sold under the trade name BEB5 3 0A80. The diglycidyl ether of bisphenol A has an epoxy equivalent of 430 to 450 g / eq and a desert content of 18.5 to 20.5 wt%. HCA stands for DOTE, 9,10-dihydro-9-oxa-10-phosphoanthracene-10-oxide, manufactured by FORTE CHEMICAL CO., LTD. Catalyst (hardening accelerator) A represents ethyltriphenylphosphonium acetate acetic acid complex, 10% soluble in methanol. Catalyst f hardening accelerator) B generation 砉 2-methylimidazole (2MI), 10% soluble ------------------------- order ----- Line (please read the note on the back before filling this page) The paper size of the table is applicable to the Chinese national standard < CNS) A 丨 Specification (210 X 297 mm) 16 15875 A7 B7 V. Description of the invention ( 17) Methyl ethyl net β gas-containing _Mobilizing agent A stands for digas diamidine, ^. Soluble in dimethyl gadolinium C, please refer to the notes on the back of M1I before filling this page) amine. Nitrogen hardener B represents the nitrogen-containing hardener produced by Hitachi Chemical Co., Ltd. under the trade name melan 9000 ™ 70 »Nitrogen-containing hardener C Synthesis Example 5. Blanket made ~~ 2—Represents Changchun Artificial Resin Factory Production, trade name BEH510, active hydrogen equivalents between 105 and iig / eqe. Related to the epoxy equivalent (EEW, Epoxy Equivalent Weight) used in this paper 'Viscosity, Solid content, system Testers according to the following test methods: ⑴Epoxy equivalent weight (EEW, Epoxy Equivalent Weight): Dissolve the epoxy resin in chlorobenzene: aerosol = 1: 1 and titrate with ΗΒγ / glacial acetic acid, according to ASTM D1652 Measured by the method, and the indicator is crystal violet. Printed by the Ministry of Economic Affairs and the Intellectual Property Bureau's Consumer Cooperative (2) Viscosity: Put the phosphorus-containing epoxy varnish in a 25 ° C thermostatic bath for 4 hours, using Bruker Brookfield viscosity meter measured at 25 ° C "(3) Solid content: Take 1 gram of varnish sample containing the phosphorus-containing epoxy resin of the present invention, bake at 150 ° C for 60 minutes The measured weight percentage of non-volatile content. The present invention will be described in more detail with the following synthesis examples and examples, but the scope of the present invention is not limited to the following synthesis examples and examples. Β Synthesis example 1: Phosphorus containing The synthetic wood paper standard of Zhi A applies to the Chinese girl standard (CNS) A4 specification (210 X 297 male S) 17 15875 A7 ______B7_____ 5. Description of the invention (is) Equipped with electric heating hood 'temperature controller' electric mixer and stirring rod , A gas inlet, a thermocouple, a water-cooled condenser, and a 5,000-necked glass reaction kettle with an addition funnel were charged with epoxy resin 1 (1000 g) and HCA (400 g). Nitrogen was added and heated After melting to 120 ° C, epoxy resin 1 and HCA are completely melted Evacuate to dry the above raw materials, then introduce nitrogen and evacuate, repeat the above steps 2 times. The temperature of the reactor is reduced to 85 to 901, and catalyst A (6'0g) is added. Start the mixer to stir the resin and catalyst evenly and Pass in nitrogen. The resulting mixture was heated to 160 ° C and held for 10 minutes. It was found that the reactant was exothermic and exothermic, heated to 1801, and maintained at this temperature for 3 hours to obtain phosphorus-containing resin A, which had an epoxy equivalent of 453 and a theoretical phosphorus content of 4.1 wt%. Synthesis Example 2 $ 4 Use the ingredients and weight listed in Table 1 below to perform the reaction in a similar manner as in Synthesis Example 1, but after the reaction is complete, add the solvents listed in Table 1 to the resulting epoxy resin to obtain a solution. State of the dish containing resin. The epoxy equivalent, solid content, and theoretical phosphorus content of the phosphorus-containing resins obtained in Synthesis Examples 2 to 4 are shown in Table 2 below. -----------! Outfitting ------- Order --------- line (Please read the precautions on the back before filling out this page) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative. ¾ Applicable * National standard bird (CMS) Al specification (2) 〇χ 297) 18 15875 A7 Λ5 258 3 _B7 V. Description of the invention (19) Table 1: Synthesis examples 2 to 4 Formulation Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 -----: t 乂 containing _ fat 3 containing filling fat C order filling resin D epoxy resin 1 (g) 1000 epoxy resin 2 (g) 1000 454.5 epoxy Wax 3 (g) 448.8 HCA (g) 320 320 145.5 Shuangfan-A (g) 139.3 4 Promoter A (g) 6.0 6.0 5.4 Two ^ § ^ 1 ^ Purpose (cake) 450 300 520.0 C (ml) 450 595 Table 2: Property analysis of phosphorus-containing epoxy resin

Fatty B, Fatty C, andro resin D, epoxy equivalent (g / eq) 403 378 451 Solid content 59.8% 60.1% 1 59.7% _ Theoretical phosphorus content 3.48% 3.48% 1.76% J Synthesis example 5: Contains rhenium The synthesis of hardened 刽 C is equipped with an electric heating mantle, temperature controller, electric mixer and stirring rod, nitrogen inlet, thermocouple, water-cooled condenser, and a 3000ml five-necked glass bottle with a funnel. 1269 grams of phenol and 37.4% formaldehyde 541.5 grams, 204 grams of melamine, and 10.2 grams of triethylamine. The temperature was raised to 80 to 85 ° C, and the reaction was performed for 3 hours. 204 g of the trimeric cavity was added and reacted for another hour. After the reaction was completed, the temperature was gradually raised to 100 ° C to remove water, and then the temperature was further increased to 120 to 1251 to react for 2 hours. After the reaction was completed, the unreacted phenol and the reaction condensation water were slowly distilled off under normal pressure, and finally kept under the air vacuum for i hours. The resulting product was a total of 984 g of gas-containing hardener B. The theoretical nitrogen content is 134 wt%, and the active argon equivalent is 125 g / eq. ('Please read the intentions on the back before filling in the reference page) Loading -------- Order ---: --------- Printed on paper scales by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (210 χ 297 public love) 19 15875 V. Description of the invention (20) f Examples 1 to 7 and comparison with you 丨 1 at room temperature in a container equipped with a stirrer and condenser Inner ', the phosphorus-containing resins B, c, and D synthesized in Synthesis Examples 2 to 4 were prepared into epoxy resin varnish according to the ratio shown in Table 3 °

Filling resin C (g)! 150 | 150 150!: J Resin containing resin D (g) 200 200 200 丨 --------—— 1 —------------ ^ Cyclopsene Resin 4 (g) 153 147: 147: 147 1 1 _ ^ 5 (g) per resin!! 1 1 丨 125 Hardener A Hardened B 65! 50 58 Additive C 65 50 Hardener D | : 65: 50 Hardening-promoting spine B 1.8 2.4 0.9 0.6 0.6 0.6 0.6 0.6 (Please read the precautions on the back of βδ before filling out this page.) Fixing:-Printed by X Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Epoxy varnish and glass fiber cloth are impregnated. After drying at 150 ° C for 120 minutes, it becomes a prepreg. The prepreg obtained is subjected to DSC (Differential Scan Calorimeter, TA2910) (temperature range 50 to 250 °). C, heating rate is 20 ° C / min) to test its glass breaking point and flame resistance after burning test. It is cut into 5 pieces of 12.5mm × 1.3mm size according to the method of UL746. Each piece burns 2 times and the total of 10 times of burning does not exceed 50 seconds, and the maximum of a single time does not exceed 丨 0 seconds, which means that the burning test has passed. The results are shown in Table 4: This paper ruler conforms to Chinese National Standard (CNS) Α 丨 Specifications (‘310 ^ 297 mm) 20 15875 A7

TgCC during average weaving) t 谙 read the precautions on the back before filling in this page) Superimpose eight prepregs on top of each other and place a 35m copper drop on top and bottom, and press at 185 ° C and 25kg / cm2 dust pressure Combined to form a laminated ship of epoxy resin and glass fiber cloth, the physical properties of each laminate are analyzed as shown in Table 5. Table 5 Analysis Items " Conditions and Specifications Example 1 Example 4 Example 7 Comparative Example 1 Combustion Test UL94-V0 Pass Pass Solder Resistance 288eC specification> 300 seconds Pass Pass Failure Peel Strength IPC Specifications> 8 lb / in 8.9 8.6 8.7 9.3 Surface Resistance IPC Specifications> 1010Ω 2.68 * 1015 1.98 * 1015 2.63 * 1015 3.57 * 1015 Volume impedance Ί IPC collar ^ < 1〇10Ω 0.89 * 1013 1.81 * 1013 1.16 * 1014 1.06 * 1014 Dielectric constant 1PC Specifications < 5.4 4.7 4.8 4.7 4.7 Escape coefficient-0.022 0.021 0.020 0.020 Tube application Examples 8 to 11 and teach you how to 丨 2 The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints it at room temperature in a container equipped with a stirrer and condenser, and prepares the ingredients shown in Table 6 in the proportion shown in the table. Epoxy varnish, paper size Using China National Standard (CNS) A4 specification (210 X 297 mm) 21 15875 A7 B7 V. Description of the invention (η) Table 6 丨 Example 8 Example 9 Example 101 Example 11: Comparative Example 2 Resin A (g) 105 1! __1 Wall Resin B (g) i 150 i 1 Filling Resin C (g) 150! Filling Resin D (g) 200! 1 Ring Resin 4 (g) 153 147 147 ... ______ j ___— Epoxy resin 5 (g)!: 125 1 ...-- 1- Hardener A (g);! j I 26.5 Hardener C (t); 68 i 65 1 68! 96 ϋ Promote Agent B (g: M 2.4 0.9 0.6 0.6 0.65 -------------- pack-(Please read the precautions on the back before filling this page) Example 8, 10, and 11 above And the epoxy resin composition obtained in Comparative Example 2 was coated on a rough surface of an 18-micron copper foil with a thickness of 80 micrometers, and dried at 15 ° C. The obtained copper foil coated with a ring-shaped resin was added to the foregoing example] The upper and lower sides of the prepreg made of epoxy resin composition were pressed at a temperature of 18.5 ° C and a pressure of 25 kg / cm2 to form a multi-layer board. The results of analyzing the physical properties of the multilayer board are shown in Table 7. β ο Magic.-. The printed circle of the Ministry of Economic Affairs, Intellectual Property Bureau, or Industrial and Consumer Cooperative Co., Ltd. See Table 7 Analysis of project conditions and specifications Example 8; ] | T2 teaching example 2 € Fire test UL 94-V0: Passed 1 Passed 丨 Passed _ Solder resistance IPC260 ° C Level 30 ________ ^ _-_. ^-4 Passed | Passed; i igi Peel strength IP 〇 ^ 6Μι (18μπι) 7.6 7.4 ------ 8.0 8.4 From the above results, it can be seen that the dish-containing wax of the present invention exhibits better burning test and soldering resistance than the filled oxygen resin, but the peel strength is also Not reduced. ¾ L degree applies to 47 countries ’national standard (Cis: S) A4 specification (210 < 297 / hair 15875 22

Claims (1)

Announcement A8B8C8D8 (B) Consumption of the Intellectual Property Bureau of the Ministry of Economic Affairs; Printed by the Agency t 6. Scope of Patent Application 0H 〇〇 \ This functional group is obtained by reacting epoxy group of epoxy resin with 9'10-diargonoxa-10-phosphoanthracene_1〇_oxide of the following formula: 0 = P-0 I Η 2. If the phosphorus-containing resin in item 1 of the scope of the patent application is made of epoxy resin and 9,10-dihydro-9-oxa-10_phosphoanthracene_1〇 • oxide and other It is prepared by reacting active argon compounds. 3. The phosphorus-containing resin according to item 2 of the patent application range, wherein the epoxy resin is selected from the group consisting of bisphenol glycidyl ether, bisdiol glycidyl ether, benzenediol glycidyl ether, nitrogen-containing glycidyl ether, Groups of glycidyl ethers of dihydroxynaphthalenes, polyglycidyl ethers of polyaldehydes and polyglycidyl ethers of polyhydroxyphenols. 4. The phosphorus-containing resin according to item 2 of the patent application range, wherein the other active hydrogen-containing compound is selected from the group consisting of amines, bisphenol resins, hydroquinones, polybasic resins, and formaldehydes. 5. For example, the phosphorus-containing resin in the second scope of the patent application, wherein the epoxy resin and | 9,10-dihydro-9-oxa · ΐ〇-phosphoanthracene-1-oxide and other paper containing active argon Again applicable _ national national standards (CNS> A4 specifications (210 X 297 public love) --- 23 15875-------------Ϊ ^ ----! | Order --J- ----- Please read the precautions on the back of the line before filling in this page) A8 B8 C8 m VI. The reaction ratio of patent application compounds is epoxy epoxy equivalent: 9 1 〇_Diazo_ 9 _ oxa -10-phosphoanthracene · 10-oxide active argon equivalent: the active hydrogen equivalent of other active hydrogen-containing compounds is 100: (5 to 50): krypton to 45). 6. A flame retardant wax composition comprising (a) a phosphorus-containing wax as described in any one of claims 1-5, (b) a hardening agent represented by formula (c) below, and (c) Hardening accelerator: r2hn (Qi read the precautions on the back before filling this page) (C) In the formula, R2 represents [(: Η2-Γ ^] ηΗ (η represents an integer from 0 to 20) or an argon atom; but at least one of R2 is not a hydrogen atom ; R1 shows NHR2, Cu alkyl or benzyl, R3 shows benzyl, naphthyl or base of the following formula: Member of Intellectual Property Bureau, Ministry of Economic Affairs ^^ Feihe ^-print A where -0 ,,- S02- 'CO-, -CH2-, -C (CH3): or the base of the formula One ch2— {5 ^ ch2 one or ν: -'_ Among the groups shown by R3 and A above, the aromatic group may be substituted with one or more selected from the group consisting of hydroxyl, amine, carboxy, and C1-6 alkyl Group. 7. The flame retardant resin composition according to item 6 of the patent application, wherein the hardening accelerator is selected from the group consisting of tertiary amine, tertiary phosphine, quaternary salt, quaternary salt, and paper. Applicable to China's national standard (J10 public love) 24 15875 Zhong 08 45 258 3 6. The scope of the application for patents The group of boron trifluoride complex, lithium compound, imidazole compound and mixtures thereof. 8. The flame retardant resin composition according to item 6 of the patent application, which may further include a member selected from the group consisting of bisphenol glycidyl ether, bisdiphenol glycidyl ether, hydroquinone glycidyl ether, nitrogen-containing glycidyl ether, An epoxy resin of a group of glycidyl hydrazone of dihydroxynaphthalene, polyglycidyl ether of polyaldehyde, polyglycidyl ether of polyhydroxynaphthalene, and the like. 9. The flame retardant resin composition according to item 6 of the patent application, which may further include a hardener selected from the group consisting of amines, bisphenol resins, resorcinol, polyhydroxy resins, and phenols. 10. The flame retardant resin composition according to any one of claims 6 to 9 in the scope of application for a patent, wherein when the ratio of the ring resin to the hardener is 100% of the epoxy equivalent of the epoxy resin, the active argon equivalent of the hardener is 2%. To 140%, and the proportion of the hardening accelerator is 50 to 50,000 ppm of the total weight of the ring resin composition. 11. If the flame retardant resin composition of the scope of patent application No. 6 is used to manufacture adhesive sheets, composite materials, Laminated boards, printed circuit boards, substrates for build-up methods, and semiconductor packaging materials. I: ----------- .Clothing --------Order ----- --- line < read the precautions on the back before filling in this page) Produced by members of the Bureau of Consumers ’Consumer Cooperatives, the paper wattage is applicable to China National Standard Apple (CNS) A4 specifications (210x297 public love _) _ 25 15875