TW500761B - Novel resin composition of phosphorus-containing compound with epoxy group - Google Patents

Abstract

This invention provides a novel resin composition of phosphorus-containing compound with epoxy group content, which includes: (1) a phosphorus-containing compound with epoxy group and (2) a phosphorus-containing hardening agent containing substitutes capable of reacting with epoxy groups. The invention further provides application of using the resin composition in preparing prepregs, composite materials, laminated products and printed circuit board. The products manufactured from the inventive resin composition have good processability and exhibit excellent flame retardancy and high heat resistance without the need for addition of a flame retardant.

Description

500761 A7 B7 V. Description of the invention (i) Field of the invention The present invention relates to a resin composition containing an epoxy group-containing phosphorus compound and its use. Products made from this composition have UL94V-0 standard flame resistance and high heat resistance, and do not contain halogen or antimony trioxide. BACKGROUND OF THE INVENTION Composite materials, especially epoxy resin materials, have been widely used in fields such as painting, electrical insulation, civil construction materials, adhesives, and laminates due to their simple processability, high safety, superior mechanical and chemical properties. . Especially for laminated boards made of epoxy resin, because these resins have strong adhesion to reinforcing materials such as glass fiber cloth, and have no volatile matter and small molding shrinkage when hardened, the resulting laminated boards have a wide range of applications. Good mechanical strength, good electrical insulation, good chemical resistance, etc., and can be widely used in electrical and electronic products. However, due to the fine lines and high density requirements of printed circuit boards, laminated boards are also required to have better mold properties, mechanical properties and heat-resistant processability. At present, the widely used FR4 laminated board has a glass transition temperature (Tg) of about 130t after hardening, so it is easy to crack in the cutting and drilling processing of more than 200 ° C in the printed circuit board manufacturing process and in the welding process above 270 ° C. Or burst. Therefore, all the parties emphasized that the laminate materials with high thermal stability and high glass transfer temperature are being actively developed. In addition, another important requirement for laminated boards is that they need to be flame resistant. Because it is often used in vehicles such as aircraft, automobiles, and public transportation, it is directly related to the safety of life and property. Therefore, the flame retardancy of printed circuit boards is absolutely necessary. (Please read the notes on the back before filling this page)

The paper size printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1 15726 500761 A7 __B7 " ~-V. Description of the invention (2) (Please read the note on the back first (Please fill in this page again for details) In order to make the laminated board flame-resistant, it is necessary to introduce a substance that can isolate the flame and reduce the combustion properties. For epoxy resin / glass fiber laminates, halogen-containing compounds, especially bromine-containing epoxy resins and hardeners, can be used, in combination with anti-flammable additives such as antimony trioxide, in order to achieve flame-retardant laminates Stringent characteristics (eg UL 9 4 V-〇 rating). However, if epoxy resin is to reach the level of UL94V-0, its bromine content needs to be as high as 17% to 21%, and antimony trioxide or other flame retardants are often used in combination. But antimony trioxide has been classified as a carcinogen; and the bromine will not only generate corrosive free radicals and hydrogen bromide during the combustion process, but aromatic compounds with high bromine content will also produce highly toxic brominated furans and brominated substances. Dioxin compounds, which seriously affect health and the environment. Therefore, the recycling and disposal of such laminated boards have problems. Based on the above, it is urgent to find a new flame retardant material to improve the environmental pollution caused by the current laminated board.

Phosphorus compounds have been widely studied and applied as a new generation of flame retardants with environmental protection. For example, use red phosphorus or phosphorus-containing organic compounds (such as triphenyl phosphate, trityl phosphate, phosphoric acid, etc.) instead of halogen compounds as flame retardants to improve the flame resistance of polymer materials or hardened resins. However, adding such compounds directly to the resin requires a large amount to achieve the effect, and it will directly affect the characteristics of the resin substrate, such as electrical properties, and cause practical difficulties. In recent years, in accordance with environmental protection and safety considerations, the use of phosphating _Resin 1 Generation_ _ i ozone resin as the formulation of flame-retardant laminates, such as US Patent 5,3 76,4 5 No. 3 using epoxy-containing compounds Phosphate esters are combined with nitrogen-containing cyclic hardeners to make laminated boards, but in order to make up for the lack of phosphorus content, it is difficult to achieve the UL 94 V-0 standard. Therefore, a variety of phosphate esters have been added for epoxidation. (210 '乂 297 mm) 2 15726 500761

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) Invention Description (3); US Patent No. 5,45 8,978 uses epoxy phosphate ester with nitrogen-containing epoxy resin and metal compound as hardener, and the finished glass is transferred The temperature is about 175 ° C, and the flame resistance is only up to the UL94V-0 edge (42 seconds vs. critical 値 50 seconds). U.S. Patent Nos. 4,973,631 and 5,086,156 use phosphine oxide derivatives with active hydrogen substituents (such as amine groups) alone or with other hardeners to harden epoxy resins; however, hardeners are used The disadvantage of introducing phosphorus into the resin is the low phosphorus content. And these two patents have not actually measured their flame retardant effect. The present inventors have made extensive investigations on the disadvantages of the prior art, and have thus completed the present invention. Detailed description of the invention The present invention relates to a resin composition containing an epoxy group-containing phosphorus compound and its use. From this composition, prepregs, composite materials, laminates, printed circuit boards, and the like having flame retardancy and high heat resistance can be obtained. The novel epoxy-containing phosphorus-containing compound resin composition of the present invention is characterized by including: (1) an epoxy-containing phosphorus-containing compound, (2)-a kind of Phosphorus hardener. The epoxy-containing phosphorus compound (sometimes also referred to as a phosphorus-containing epoxy resin) used in the resin composition of the present invention is a compound having the following structure: Formula (Human --------- ------------------ one by one ------ one 0

0H

X

0H (Please read the precautions on the back before filling this page) -------- Order— 丨

HzC-CH-CH2-fT-A.T ^ CHz iHCH.T.A This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 3 (correction page) 15726 500761 A7 B7

V. Description of the invention (4) 0 n, -TAT-CH2CHCH2 (where m '= l to 11, n' = l to 11, x = 0, S or electron pair, T can be the same or different, respectively Represents · 0 A can be the same or different, respectively -NH- or -C00- @ ιΰ © © -t-ο ο (Please read the precautions on the back before filling out this page) ch3 'a: · — (Ciz ) — ^ Si-Oj-Si—

Gii

Ci: 5 Gt3

Ri R2: alkyl, (^ .4 alkoxy

^ # -Q

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R] and alkyl, Υ = Η or OH and r = l to 10, and s = l-10. ) Formula (B): Λ ί, Γ. Γ. CH: CHCH: Seven T, Α-Τ. [Τ-Α -jv · τ. C KK: C κ C Η :. Τ-A. Τ · C Η : C Η C Η:-} ν-XR, Ο 丄 I 丨 一 / \-Τ-Α τ-Ρ-τ. A -jf% .-T-CH: CHCH,

I k · (where m '= 1 to 1 1, ιΓ = 1 to 1 1, χ = 0, S, or electronic pair, the paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 4 (revision page) 15726 500761 A7 B7

Amend to add her January T. V. Invention Description (5) T can be the same or different, respectively representing -〇 ·, _ec > a A can be the same or different, respectively representing .f3 0¾

Si-olsi- ^ R:. (¾ / s Ci3 (Please read the precautions on the back before filling in this page) = Academy, ¢ ^ .4

The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed R! And Alkyl, Y = H or OH and r = 1 to 10, and s = 1 to 10. The above two types of phosphorus-containing epoxy compounds are prepared by the addition reaction of an epoxide with a compound having an active group. Wherein the compound (A) can be a compound represented by the following formula (C): Γ ί λ-λ-τ -ρ-τ -a k k, ·-T 1 X = P—R · 1—A—Z2 .. ..... (C) (where m = 0 to 10, X = 0, S, or electron pair, T can be the same or different, respectively representing -O-, -NH- or -coo- China National Standard (CNS) A4 Specification (210 χ 297 mm) 5 15726 ------- Order --II-I I-- · 500761 丨 Amend A7 B7 Supplement V. Description of Invention (A can be the same or can be Different, respectively represent ◎ -0 old 0 .CS3 Qc ^} ch3 — (CK?); 〇 {3 ch3 Ί \ I Si — ofsi-ί l ί (¾ / s (¾ is; R '= 1.4 焼) , Ci.4 ethoxy R! And alkyl, Y = H or OH and r = 1 to 10, s = 1-10 Z! And Z2 = -〇H, -NH2, -SH and -COOH.); Addition reaction with compound (E) containing at least 2 epoxy groups to obtain:

Ο 0! \ 1 \. H: c-ch-ch2 — 丁-A, T, -CK: CHCK (E) — * ------------------ ^ — ------ (Please read the notes on f. And then fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-1 z1

A. The foregoing is the same as the definition of C, and the X "

B

T

P · — R

T person ο 11 to ο Η m ^ Chinese where χ = 〇, S or electron pair,

The manifestation of compounding \ ly D VA η ρ · -ptj

T 2 ζ ·

D This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 6 (Revised page) 15726 500761 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) T can be the same as Can be different, respectively representing -0-, -NH- or -C00- 'A can be the same or different, respectively representing 〇 广' ο ο © -C ^ g)

Ci3 (¾ Oi3 · — (Gt?) —-^ Si—Oj-Si—

Oil, ^ CH: ^ 0: 3 to alkyl, (^ .4 alkoxy, γ γ rr Α. 4; R! And alkyl, Y = H or OH and r = 1 to 10, S = 1- 10, Z \ and Z, 2 = -OG, -NHG, -SG, and -COOG, where G = CH2CHCH2); addition to compound (F) containing at least two reactive groups that can react with epoxy groups It is obtained by reaction: HTATH (F) (wherein Η represents a hydrogen atom and other symbols are as defined above); wherein compound (D) can be obtained by epoxidation of compound (C) with epihalohydrin. The above addition reaction may be a solvent-free melting reaction or an H reaction in the presence of a solvent. In this reaction process, no halogen-containing compound is used. The compound containing at least two epoxy groups used in this reaction means an epoxy compound having a difunctional group and a polyfunctional group. For example, bisphenol, fluorene, benzene difluorene, biphenol, naphthalene, hydrocarbons, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 7 (correction page) 15726 -, ---- ---- 1111-III--I — ^ «— — — 1 —--- (Please read the notes on t-page and fill out this page) 500761 A7 B7 V. Description of the invention ( 8) The diglycidyl ether of bisphenol may be one having -Ph-X-Ph- (in this group, X represents · <: Η2-, -C (CH3) 2-, -CH (CH3)-,- 〇-, -s-, -c (o)-, -S02-, etc.), examples of which include bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether , Tetramethylbisphenol A glycidyl ether, tetramethylbisphenol F glycidyl ether, tetramethylbisphenol AD glycidyl ether, tetramethylbisphenol S glycidyl ether, and the like. Examples of the glycidyl ether of biphenol include, for example, 4,4'-biphenol glycidyl ether, 3,3'-dimethyl-4,4'-biphenol glycidyl ether, 3,3 ', 5,5' -Tetramethyl-4,4'-biphenol glycidyl ether and the like. Examples of the glycidyl ether of hydroquinone include, for example, resorcinol glycidyl ether, hydroquinone glycidyl ether, isobutyl hydroquinone glycidyl ether, and the like. Examples of the polyglycidyl ether of novolac include, for example, novolac polyglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A novolac polyglycidyl ether, and the like. Examples of polyglycidyl ethers of other polyphenols include, for example, ginseng (4-hydroxyphenyl) 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-hydroxyphenyl) ethane polyglycidyl ether, __ ((3,5-1 ^ methyl-4-Xiangyl phenyl) ethyl ether polycondensation Glycery Charm Temple. Mixtures of the various glycidyl ethers described above may also be used.

Among the above glycidyl ethers, the bisphenol A with a bifunctional group is preferred (please read the precautions on the back before filling this page)

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 8 15726 500761 Α7 Β7 V. Description of the invention (9) Polyglycidyl ether, resorcinol Glycidyl ether, etc., tri-functional ginseng (4-hydroxyphenyl) methane polyglycidyl ether, etc., tetra-functional (4_ hydroxyphenyl) ethane polyglycidyl ether, cresol novolac polycondensation Compounds such as glyceryl ether or mixtures thereof. Examples of compounds containing at least two reactive groups which can react with epoxy groups in the above addition reaction may be, for example, amines, bisphenols, hydroquinones, polyphenols, phenols, amidines, olefins, cyclic hydrocarbons, Nitrogen heterocycles, siloxanes, polysoxanes, polythiols, polycarbonates, etc. or mixtures thereof. Examples of suitable amines include, for example, diaminodiphenylmethane, poly amine, and the like. Suitable bisphenols are those having -Ph-X-Ph- (in this group, X shows -CH ^, • C (CH3) 2-, -CH (CH3)-, -〇-, -s-, -c (0) -'- S02-etc.), Gan, which

Examples include bisphenol A, bisphenol F, bisphenol ad, bisphenols, tetramethyl phenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, 4, 4, Bisphenol 3, 3, -dimethyl-4J [,-Bisphenol, 3,3 ', 5,5, -tetramethyl-4 ,, phenol, etc. Examples of suitable hydroquinones include, for example, m-phenol ί Packs diphenol, hydroquinone; phenol, isobutyl hydroquinone, etc. Examples of suitable polyhydric phenols include, for example, ginseng (4-hydroxyphenyl) octane, ginseng (4-hydroxyphenyl) ginseng (4-hydroxyphenyl) propane, ginseng (4 · hydroxyphenylalkane, ginseng ( 3-methyl_4_hydroxyphenyl) methane, ginseng (3 $ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Dimethyl-4-hydroxyphenyl) Methane, methyl-hydroxyphenyl) ethane, methyl (3,5 · dimethyl · 4 · hydroxyphenyl) ethane, etc. Examples of suitable phenolics include, for example, phenol-formaldehyde condensates, paper sizes, and applicable Chinese National Standard (CNS) A4 specifications (210X297 mm) 15726 9 500761 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (10) Aldehyde condensate and bisphenol A novolac condensate. Among them, bifunctional bisphenol A, bisphenol F, tetramethylbisphenol hydrazone, 4,4'-biphenol'3,3, _dimethyl_4,4, -biphenol, 3 , 3,, 5,5, -tetramethyl-4,4'-biphenol and trifunctional reference (4-hydroxyphenyl) methane and tetrafunctional (4-hydroxyphenyl) ethane and Cresol novolac, etc. In the above addition reaction, the use ratio of the compound containing an active group capable of reacting with epoxy groups and the epoxy compound containing at least two epoxy groups is preferably 5-95: 95-5 by weight, and preferably 10- 90: 90-10 weight ratio, more preferably 20-80: 80-20 weight ratio, and most preferably 30-60: 70-40 weight ratio. In this reaction, a catalyst may also be used. Examples of the catalyst are, for example, tertiary amines, tertiary phosphines, quaternary ammonium salts, quaternary scale salts, complex salts of boron trifluoride, lithium compounds, imidazole compounds, and the like. These catalysts can be used alone or in combination. Among them, tertiary phosphine and quaternary scale salts are particularly preferred, especially triphenylphosphine, ethyltriphenylphosphonate salt, acetic acid complex, and butyltriphenylphosphonium bromide. The amount of the catalyst used is preferably 50 to 50,000 ppm for the reactant, preferably 100 to 30,000 ppm, more preferably 200 to 10,000 ppm, and most preferably 500 to 2,000 ppm. If the catalyst is added in excess, the reaction time can be shortened, but by-products are easily generated and the application of the product is adversely affected. For example, when it is used in a circuit board laminate, the electrical properties, moisture resistance, and water absorption are all deteriorated; if the amount of catalyst added is too small, the reaction speed is too slow, which is not conducive to industrial use. ________________________ ________________________________________ — This addition reaction should be carried out at a temperature of 20 to 300 ° C, preferably 50 to 250 ° C, more preferably 100 to 220 ° C, and most preferably 100 to 190 ° C. If the reaction temperature is too high, it is easy to generate by-products and it is difficult to control the reaction speed. (Please read the precautions on the back before filling this page)

, 1T

This paper scale applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) 15726 500761 Μψ. --ST-11 11 Description of the invention (may accelerate the degradation of the resin; if the reaction temperature is too low, the reaction efficiency is poor and The obtained resin is difficult to meet the requirements of high temperature use. The phosphorus-containing compound containing an epoxy group used in the present invention can be used alone or mixed with other phosphorus-free epoxy resins. The phosphorus-free epoxy resins such as Compounds represented by phenol, phenol, naphthalene, olefin, cyclic hydrocarbon, nitrogen-containing heterocyclic ring, phenols, siloxane, polysiloxane, or HO-Ph-X-Ph-OH (wherein, Ph is phenyl, X shows glycidyl ether, glycidylamine, -CH2-, -C (CH3) 2-, -CH (CH3)-, -0-, -s-, -c (0)-, -so2-, etc.) , Glycidyl sulfide, glycidyl carboxylate, etc. In the present invention, modified epoxy resins, such as oxazolidinone modified epoxy resin (Angew · Makromal. Chem., Vol. 44, ρρ151, 1975) and melamine modified epoxy resin, etc. In the present invention, other low-molecular-weight phosphorus-containing epoxy resins can also be mixed and used. Grease to adjust the physical and mechanical properties of the resin. This low molecular weight phosphorus-containing epoxy resin is known to be synthesized by a variety of methods, for example, disclosed in Zhu. Obsch. Khim., Vol. 54, pp2404, 1 9 8 4; Sho 5 1 -1 4 3 6 2 0; the method disclosed in U.S. Patent No. 2,8,56,369. The phosphorus-containing hardening agent having a substituent capable of reacting with epoxy groups used in the present invention is represented by the aforementioned formula (C). In addition to the above components, the resin composition of the present invention may be used in combination with a conventional phosphorus-free hardener, if necessary, depending on the composition, which is the most phosphorus-free hardener in the present invention. Includes, for example, phenolic lacquers and bisphenols, phenols, naphthalenes, olefins, cyclic hydrocarbons, nitrogen-containing heterocycles, siloxanes, polysiloxanes, and J > hX containing at least two hydroxyl, amine, mercapto, and carboxyl groups -Ph --------> -------------- Order ------------(Please read the precautions on the back before filling in this page) Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 11 (Amended Page) 15726 500761 A7 B7 'Weng; Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Compounds shown in the description of the invention (12) (where X is -ch2-, -C (CH3) 2-, -CH (CH3)-,- 〇-, -s-, -c (o)-, -so2-, etc.), etc. The addition amount of the above-mentioned phosphorus-free hardener is 0 to 95% by weight, and preferably 0 to 95% by weight of the total amount of the hardener. Examples of hardeners containing at least 2 amine groups by weight include, for example, dicyandiamine (DICY), diaminodiphenylmethane (DDM), diethyltriamine (DETA), diaminodiphenyl Base maple (DDS), m-phenylene diamine (MPDA), etc. Examples of the hardener containing at least two carboxyl groups include, for example, maleic anhydride (MA), phthalic acid (PA), hexahydrophthalic anhydride (HPA), tetrahydrophthalic anhydride (THPA), and the like. Examples of the hardener containing at least 2 hydroxyl groups include, for example, ginseng (4-hydroxyphenyl) methane, ginseng (4-hydroxyphenyl) ethane, ginseng (4-hydroxyphenyl) propane, ginseng (4-hydroxybenzene) Base) butane, ginseng (3-methyl-4-hydroxyphenyl) methane, ginseng (3,5-dimethyl-4-hydroxyphenyl) methane, ethane (4-hydroxyphenyl) ethane, ethane (3,5-dimethyl-4-hydroxyphenyl) ethane and the like. Examples of the hardening agent containing at least 2 fluorenyl groups include, for example, m-phenylene dithiol, dimethyldiphenyl maple, ginseng (4-mercaptophenyl) methane, ginseng (4-mercaptophenyl) ethane, ginseng (3-methyl-4-fluorenylphenyl) methane, and (3,5-dimethyl-4-fluorenylphenyl) ethane. Examples of suitable novolac resins include, for example, phenol formaldehyde condensates, cresol novolac condensates, and bisphenol A novolac condensates. The amount of hardener added depends on the reactive hydrogen equivalent of each hardener and the epoxy equivalent of the phosphorus-containing compound containing epoxy groups, the epoxy equivalent of the phosphorus compound containing epoxy groups and the reactive hydrogen of the hardener The equivalent ratio is from 0.5: 1 to 1.5: 1, preferably from 0.7: 1 to 1.3: 1. The resin composition of the present invention can be used in applications in the field of high heat resistant materials, such as laminates, printed circuit boards, 1C sealing materials, high heat resistant powder coatings, engineering plastics, and the like. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 12 (correction page) 15726 -II — — If — — — — — i IIIIII ^ --— — — — — — (I Read the notes on the t side and fill out this page) 500761 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) In the resin composition of the present invention, hardening accelerators, solvents and other additives may be added as required . The hardening accelerator used in the present invention is, for example, a tertiary amine, a tertiary phosphine, a quaternary ammonium salt, a quaternary scale salt, an imidazole compound, and the like. These hardening accelerators may be used alone or in combination of two or more. The tertiary amine includes, for example, triethylamine, tributylamine, dimethylamine ethanol, ginseng (N, N-dimethylaminomethyl) phenol, N, N-dimethylaminocresol, and the like . Tertiary phosphines include, for example, triphenylphosphine. Quaternary ammonium salts include, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, trimethylbenzyl ammonium chloride, trimethylbenzyl ammonium bromide, trimethyl iodide Benzyl ammonium, etc. Quaternary scale salts include, for example, tetrabutyl chloride scale, tetrabutyl scale bromide, tetrabutyl scale iodide, tetrabutyl iron acetate complex, tetraphenyl chloride scale, tetraphenyl scale bromide, iodine Tetraphenyl scale, ethyl triphenyl scale, ethyl triphenyl scale bromide, ethyl triphenyl scale iodide, ethyl triphenyl scale acetate complex, ethyl triphenyl scale Phosphate complex, propyl triphenyl chloride scale, propyl triphenyl bromide scale, propyl triphenyl iodide rust, butyl triphenyl chloride scale, butyl triphenyl scale, Butyl triphenyl iodide scale. Imidazole compounds include, for example, 2-methylimidazole, 2.phenylimidazole, 2-ethyl-4-methylimidazole, 2-dodecylimidazole, and 2-heptadecylimidazole. The preferred hardening accelerators are imidazole compounds and quaternary scale salts', especially 2 · methylimide ^ 2-phenylimidazolium, ethyltriphenylrust-acetic acid complex and bromobutyltriphenylscale. The amount of the hardening accelerator is preferably from 0 to 5.0% by weight based on the total weight of the composition, preferably from 0.01 to 4.5% by weight, and more preferably from 0.1 to 4.0% by weight. Standard (CNS) A4 specification (210 X 297 mm) 13 (correction page) 15726 — I »— — — — — — — — — — — — — — I — ^ 1111111 · Read the phonetic notation on t side? Please fill in this page again) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 500761: Ar η γψ _ ^ Ώ7 / 丨 5. Description of the invention () It is best to be 0.15 to 3.0% by weight. Although the hardening accelerator used in the present invention also includes a halogen-containing compound, its use amount is very low and has no substantial effect. The amount of hardening accelerator used in the present invention is generally from 0.01% to 5.0% by weight. The halogen content of the produced product is very low (for example, less than 200 ppm) and meets the requirements of halogen-free substrates (halogen If the detection amount is less than 900ppm, it will reach the industry standard). In the composition of the present invention, the viscosity of the composition can be adjusted by adding a solvent, and the viscosity range should be adjusted to 20 to 500 cpS / 25 ° C. The viscosity measurement is to place the composition in a 25 ° C constant temperature bath for 4 hours, using Brookfield ( Brookfield) viscometer was measured at 25 ° C. Usable solvents are, for example, organic aromatic hydrocarbons, ketones, protic solvents, ethers and esters. Organic aromatic hydrocarbons include, for example, toluene and xylene. Ketones include, for example, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Protic solvents include, for example, N, N · dimethylformamide, N, N · diethylformamide, and dimethylimine. The ethers include, for example, ethylene glycol monomethyl ether and propylene glycol monomethyl ether. The esters include, for example, ethyl acetate, ethyl isopropylate. Other additives that can be used in the present invention are additives commonly used in the art, such as modifiers, heat stabilizers, light stabilizers, ultraviolet light absorbers, and plasticizers. The present invention also relates to the use of the resin composition of the present invention, including use in the field of high heat-resistant materials, such as laminated bodies, integrated circuit sealing materials, high heat-resistant powder coatings, engineering plastics, and the like. The resin composition of the present invention can also be made into a prepreg by impregnating the substrate. For the impregnation substrate, organic or inorganic materials such as paper, glass, metal, carbon fiber, boron fiber, cellophane, and organic polymers can be used. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) " " 14 (correction page) 15726 --------------------- Order --------- ^ 一 ^ " (Please read the precautions on side A before filling out this page) 500761 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling out this (Page) The resin composition of the present invention can be made into a package according to a conventional method, and includes a laminate of a copper foil, a fiber support, and the resin composition of the present invention. For example, a glass fiber cloth can be impregnated into the resin composition of the present invention, and then the fiber cloth can be dried by heating to obtain a dry prepreg. The obtained prepreg can be stored at room temperature for several months, and has excellent storage properties. This prepreg can be further formed into a composite laminate, or it can be used as an adhesive layer for prepreg, or after one or more prepregs are combined, they can be placed on one or both surfaces. The copper foil was heated with pressure to obtain a laminated board. The dimensional stability, chemical resistance, corrosion resistance, moisture absorption and electrical properties of the obtained laminated board are far superior to the standards of current products, and are suitable for making electrical products such as electronics, space and transportation, and Used to manufacture printed circuit boards and multilayer circuit boards. In summary, the present invention provides a novel epoxy group-containing phosphorus-containing resin composition having excellent flame resistance, thermal stability, and mechanical properties, and uses thereof. The present invention will be described in detail by the following examples, but these examples are only used to illustrate the present invention and not to limit the scope of the present invention. The epoxy equivalent and solid content in the following are measured according to the following methods: Epoxy Equivalent Weight (EEW) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: the epoxy resin is dissolved in chlorobenzene: chloroform = 1: In the solvent of 1, titration with HBr / glacial acetic acid was carried out according to the method of AS TMD 1652, and the indicator was crystal violet. Solid content: The weight percentage of the non-volatile matter measured by taking a sample of epoxy resin composition and baking it at 150 V for 60 minutes. The types of epoxy resin used in the following are as follows: Epoxy resin 1: The diglycidyl ether of bisphenol A produced by Changchun Artificial Resin Factory and sold under the trade name BE 1 8 SEL. Its epoxy equivalent is applicable to the paper standard. China National Standard (CNS) A4 specification (210X297 mm) ~ ~~ 500761

5. Description of the invention (10) It is between 185 and 195 g / eq, the hydrolyzable chlorine is below 200 ppm, and the viscosity is between 11,000 and 1 5,000 cps / 25 ° c. (Please read the notes on the back of vg before filling this page) Epoxy Resin_ 5: Glycidyl ether of resorcinol, its epoxy equivalent is 1 15 to 125g / eq. ): The product obtained by the reaction of phosphonium chloride (POCl3) with phenol and m-xylylenedihydrazone, whose hydrogen-oxygen equivalent is 250-280g / eq. Synthesis Example 1: Phosphorus-containing epoxy resin A was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and used a 3 liter five-necked flask as a reaction vessel. The flask was equipped with a device for controlling and displaying temperature and pressure, and could be used for water, A co-distilled mixture of epihalohydrin is condensed and separated into a water phase and an oil phase. A flask is charged with 600 g of hydroxyphenyl phosphate (A) and 1 245 g of epichlorohydrin. The resulting mixture is stirred under atmospheric pressure until After homogeneous dissolution, warm to 70 ° C under the absolute pressure of 190mmHg, and add 2 1 8.8 8 g of 4 9.3% sodium hydroxide solution at a certain rate within four hours at the equilibrium temperature and pressure of the solution. The water in the reactor is distilled off in an azeotropic manner. After condensing, the azeotrope is separated into an oil phase and a water phase. The oil mash is continuously returned to the reaction system, and the water phase is discharged from the reaction system. After the reaction was completed, the residual epichlorohydrin and the solvent were distilled off under reduced pressure. The obtained crude epoxy resin was dissolved in a solution of methyl ethyl ketone and deionized water, and sodium chloride in the resin was washed with water, and then methyl ethyl ketone was distilled off under reduced pressure to obtain 795 g of light The brown phosphorus-containing ring gas resin A has an epoxy equivalent of 3 5 7. Synthesis Example 2: Synthesis of phosphorus-containing epoxy resin B. A 1-liter five-necked glass bottle equipped with an electric heating cover and a temperature controller was used as a reaction kettle. The middle neck of the glass bottle was equipped with an electric mixer and stirring 16 (correction page X [572 'This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 500761 Repair without B7 V. Description of the invention (17) (Please read the notes on the back and fill in this page again) Stick, side A thermocouple and a water-cooled condenser are respectively installed on the two necks, and a nitrogen inlet and a feeding neck are respectively provided on the other two necks. 300 g of hydroxyphenyl phosphate (A) and 264 g of ring gas resin 1 are added from the feeding necks. Pass in nitrogen and heat the glass reactor to 120 ° C. After the above materials are completely melted, vacuum dry at the same temperature, repeat the steps of nitrogen and dry twice. Reduce the temperature of the reactor to 80 ° C. After adding 0.52 g of a 10% ethyl triphenylscale acetic acid complex methanol solution as a catalyst, the reaction kettle was heated to 160 ° C and reacted for 120 minutes to obtain a phosphorus-containing epoxy resin B. The oxygen equivalent is 1275. Synthesis Example 3: Phosphorous epoxy resin C A 1-liter five-necked glass bottle equipped with an electric heating hood and a temperature controller was used as the reaction kettle. The middle neck of the glass bottle was equipped with an electric mixer and a stirring rod. The two necks on the side were equipped with thermocouples and water-cooled condensation. The other two necks are the nitrogen inlet and the feed neck. From the feed neck, add 100 grams of phosphorus-containing epoxy resin A and 7.82 grams of resorcinol, pass in nitrogen and heat the glass reactor to 120 ° C, so that After the phosphorus-containing epoxy resin A and resorcinol are completely melted, they are vacuum-dried at the same temperature, and the steps of introducing nitrogen and vacuum-drying are repeated twice. 0.06 grams of triphenylbenzene is printed and added by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Phosphine was used as a catalyst, and the reaction temperature was raised to 175 ° C. After 1 hour of reaction, phosphorus-containing epoxy resin C was obtained, and its epoxy equivalent was 1 1 67 〇he. 1_ Example 1 4 phosphorus-containing epoxy i-lipid The synthesis of D uses a 1-liter five-necked glass bottle equipped with a heating cover and a temperature controller as a reaction kettle. The middle neck of the glass bottle is equipped with an electric mixer and a stirring rod. The two necks on the side are equipped with thermocouples and water-cooled condensation, respectively. Device, the other two necks are separately Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 17 (revised page) 15726 500761 A7 V. Description of invention (18) (Please read the precautions on the back before filling this page) For the nitrogen inlet and feed neck .Add 100 g of phosphorus-containing epoxy resin A and 15.35 g of bisphenol A from the feeding neck, pass in nitrogen and heat the glass reactor to 120 ° C, after the phosphorus-containing epoxy resin A and bisphenol A are completely melted , Vacuum drying at the same temperature, and then repeating the steps of nitrogen and vacuum drying twice. Add 0.06 g of triphenylphosphine as a catalyst, and raise the reaction temperature to 75. 〇 After 1 hour of reaction, a phosphorus-containing epoxy resin D was obtained, and its epoxy equivalent was 897. Synthesis Example 5: Synthesis of phosphorus-containing epoxy resin E uses a 1-liter five-neck glass bottle equipped with an electric heating cover and temperature controller- as a reaction kettle. The middle neck of the glass bottle is equipped with an electric mixer and a stirring rod. The two necks are respectively equipped with thermocouples and water-cooled condensers, and the other two necks are nitrogen inlets and feed necks, respectively. Add 125.0 grams of phosphorus-containing epoxy resin A and 20.0 grams of hydroxyphenyl phosphate (A) from the feeding neck, pass in nitrogen and heat the glass reactor to 120 ° C, after the above materials are completely melted, pump at the same temperature. The acetone in the phosphorus-containing epoxy resin A was vacuum-recovered, the raw materials were completely dried, and then the steps of introducing nitrogen and vacuum-drying were repeated twice. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, added 0.06 g of triphenylphosphine as a catalyst, and raised the reaction temperature to 75 ° C. After 1 hour of reaction, phosphorus-containing epoxy resin E was obtained, and its epoxy equivalent For 293. ^ Synthesis Example 6: Synthesis of phosphorus-containing epoxy resin F uses a 1-liter five-necked glass bottle equipped with an electric heating mantle and a temperature controller as a _reaction kettle '. The middle neck of the glass bottle is equipped with electric stirring J and a stirring rod. The two necks on the side are respectively equipped with a thermocouple and a water-cooled condenser, and the other two necks are respectively a nitrogen inlet and a feeding neck. Add 50 grams of hydroxybenzene from the feeding neck. The paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 18 (revised page) 15726 500761 5. Description of the invention (19) Phosphate (A) and 82.6 grams For epoxy resin 5, nitrogen gas was passed through and the glass reaction kettle was heated to 120 ° C. After the above materials were completely melted, vacuum drying was performed at the same temperature, and then the nitrogen gas was passed through the steps and vacuum drying was repeated twice. After reducing the temperature of the reaction kettle to 80 ° C, adding 0.50 g of 10% ethyltriphenylphosphonate acetic acid complex as a catalyst, the reaction kettle was heated to 160 ° C and reacted for 120 minutes to obtain a phosphorus-containing epoxy Resin F had an epoxy equivalent of 272. The formulation of the epoxy resin composition of the present invention is shown in Examples 1-6 in Table 1. Comparative examples 1 and 2 are control groups. At room temperature, blend the phosphorus-containing epoxy resin synthesized above with the hardener, hardening accelerator, and solvent according to the addition ratio shown in Table 1 to form a phosphorus-containing epoxy resin composition: (Please read the precautions for f side first (Fill in this page again),? Τ Print the composition of each example and comparative example in Table 1 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy. Composition formula (g) Example 1 Example 2 Example 3 Example 4 Example Example 5 Comparative Example 1 Comparative Example 1 Example 2 Phosphorous epoxy resin B 150.0 150.0 Phosphorous epoxy resin C 128.3 Phosphorous epoxy resin D 140.8 Phosphorous epoxy resin E 133.1 Phosphorous epoxy resin F 125.0 Epoxy resin 2 * 47.5 47.7 38.1 Epoxy resin 3 ** 125 Epoxy resin 4 *** 125 Hydroxyphenyl phosphate 〇Π Π Q 1 Ί 38.40 12.50 48.00 — (A) y u. V7 οιτί Hardener 26.61 27.8 30.8 14.23 17.15 250 260 Hardening accelerator 10% 2-methylimidazole in DMF solution 1.35 0.89 1.30 2.1 1.83 1.15 0.625 0.625 This paper size applies Chinese National Standard (CNS) A4 regulations Grid (210X297 mm) 19 15726 500761

V. Description of the invention (2G) Note: (Please read the notes on the back before filling in this page) *: Epoxy resin 2 represents the polymer of cresol-phenolic condensate produced by Changchun Artificial Resin Factory and sold under the trade name CNE200A80. Glycidyl ether has an epoxy equivalent of 200-220 g / eq, a solvent of acetone, and a solid content of 79.0-8 1.0 wt%. : Epoxy resin 3 represents the diglycidyl ether of tetrabromobisphenol A produced by Changying Artificial Resin Factory and sold under the trade name BEB 5 3 0A80. Its epoxy equivalent is between 43 0-450g / eq. At 18.5_ 2Ό · 5 wt% 〇 *** · Ring gas resin 4 represents the diglycidyl ether of tetrabromobisfluorene A produced by Changchun Artificial Resin Factory and sold under the trade name BEB 526A80. Its epoxy equivalent is between 410 -430g / eq, bromine content between 19.0-2 1.0 wt% ○ ****: Hardener A represents 10% DMF solution of dicyandiamide. Piece quality test Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, impregnated the glass fiber cloth with the phosphorus-containing epoxy resin composition prepared in the above examples and comparative examples, dried at 150 ° C to become a prepreg, and then DSC (Scanning calorimeter, TA2910) (differential scanning calorimeter, TA2910) was tested for its glass transition temperature, and its flame resistance was tested by a fire test. The results are shown in Table 2. From Table 2, it can be seen that the composition made by the composition of the present invention is The prepreg is flame retardant and the glass transition temperature is greatly increased. Table 2 Flame retardancy and glass transition temperature of prepreg after baking at 180 ° C for 120 minutes. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 2〇 (correction page> 15726 5 is

7 7 AB 1 Γ > Ⅴ. Description of the invention (21) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Burning Test Passing Passing Passing Passing Passing Passing Passing Passing Tg (I) ° c 169 174 192 187 158 173 132 150 Note: * flame test: According to UL94 V-0 method. Eight pieces of the above-mentioned various prepregs were stacked respectively, and a piece of 35 micron copper foil was placed above and below, and the laminate of the prepreg was pressed and laminated at a temperature of 185 ° C and a pressure of 25 Kg / cm2. As shown in Table 3, it can be known from the table that each test item of the composition of the present invention can meet the required standards. Table 3 Test results of physical properties of the substrate after heating and pressing (please read the precautions on the back before filling this page) · Analysis item conditions and specifications Example 3 Example 5 Comparative example 1 Comparative example 2 Solder resistance IPC 260 ° C Specifications > 30 seconds pass pass peel strength IPC specifications > 8 lb / in 8.92 8.56 9.25 8.90 surface resistance IPC specifications > 1〇12 2.78 * 1015 2.36 * 1015 2.88 * 1015 3.57 * 1015 bulk resistance IPC specification ^ 01 ° 2.10 * 1013 2.02 * 1013 1.16 * 1014 1 · 06 * 1014 Dielectric constant 1 卩 (: Specifications < 5.4 4.45 4.81 4.72 4.60 Diffusion factor-0.021 0.023 0.022 0.020 Order ---------- line-- 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics. In summary, the prepreg and its laminate made of the composition of the present invention are flame-resistant and the glass transition temperature is as high as more than 190 ° C. The solder resistance, peel strength, surface resistance, bulk resistance, dielectric constant, and dissipation factor of the finished product also meet the requirements of the specification or even better. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 21 (Correction page) 15726-· 1 n ϋ 1_1 ϋ ϋ I ϋ n '

Claims (1)

_H3_ ~ No. 4 05991 Patent Application rr iff Patent Range Amends Our Factory ..._ .. __. ',,, .. d | >> "Day) A phosphorus-containing resin composition containing epoxy groups, Including j (1) epoxy-containing phosphorus-containing compound of formula (A) or formula (B): Formula (A): L · .. 〇 OH X OHl \ I ii | H2C-CH-CH2-fT-AT -CH2CHCHjT-A-fT-PT-A .T-CH: CHCH2 ^ -ί R, Ο; -TaT-CHjCHCH: (where m, = l to 1 1, n, = l to 1 1, x = o, s, or electronic pair, τ can be the same or different, respectively representing -0-, -NH-, or -COO, A can be the same or different, respectively, and printed on behalf of ch3, 〇ί3 (¾-(CHi) — -l · Si-Oj-Si- ch3 vch3 / s ch3 R ,,%] alkyl, (v4 alkoxy, Ri Ri ro .0 This paper size applies the Chinese National Standard (cNS) A4 specification (210 X 297 male cage) 1 15726 500761 H3 I and alkyl, Y = H or OH and il to 10 s = 1-1 0); Formula (B): Ο X OH OH CH 2 CHCH: -Η · τ-A-T · Bu T-Af e-τ · CH 2 CHC Η 2 u · T-H 2 CHCH 2 Seven ·-Λ IXR · 1., -A -fT-PT.A- + e.-T * CH1CHCH2 I Rf (where m '= l to 11, n' = l to 11, x = o, s, or electron pair, T = can be the same or the same Different, respectively -0-, -NH- or -COO The A printed by the Employee Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs may be the same or different. It represents (§) ο 〇ί3 〇ί3 (¾1-A_〇U- 名-(CH2) r Οί3 XCHi / s 〇i3 R ' = Yuanji, C ^ .4 0 Ri 0 This paper size applies to China National Standard (CNS) A4 specification (210X297 male cage) X .0 15726 500761 H3 Ri and alkyl, Y = H or 〇H and r = 1 to i〇, s = 1 to 1 〇 ); (2) a phosphorus-containing compound having a substituent capable of reacting with epoxy groups as a hardener, wherein the ratio of the epoxy equivalent of the phosphorus-containing compound containing epoxy groups to the reactive hydrogen equivalent of the hardener is 0.5 ·· 1 to 1.5: 1. 2. The phosphorus-containing resin composition according to item 1 of the scope of patent application, wherein the compound of formula (A) is a compound represented by the following formula (C): λ D XUPIR T 2 ZIAI τI X »ρ IRfI -TA1AJ to ο II m Chinese formula ο I represents the generation of different types,,,, cocoa or heterogeneous phase cocoa or S cocoa XTA or Η-Ν ο ο (§1 0 Ri Ri CH3 s ch3 — (CH2); Oi3 ch3 ch3 1 〈卜 〇 一一 ^ Ministry of Economic Affairs t Central Standard Staff Welfare Workers will print alkyl, Cm alkoxy Y 0 Q This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 3 15726 500761 H3 Ri and R2 = (V4 alkyl, Y = H or OH and r = 1 to 10 redundant 1 and Z2 = -〇 H '· ΝΗ2, -SH and -COOH); obtained by addition reaction with a compound (E) containing at least 2 epoxy groups. 〇 〇 (E) • (D) / \ / \ H ^ C- CH-CHj-T ^ AT-CHjCHCH: (In the formula, the definition of each symbol is the same as above); The compound of formula (B) is a compound represented by the following formula (D): tr? Ί χ 2 i-Α — T —T one person one T one P —T — Α · — Z * 2 · · R, 丄 1 (where m = 0 to 10, 4 15726 500761 _H3_ R! And alkyl, Y = H or OH and r = 1 to 10 1-10 ^ Z, ι and Z, 2 = -OG, NHG, -SG and -COOG, where G = CH2CHCH2) \ J Addition reaction with compound (F) containing at least 2 reactive groups that can react with epoxy groups: Η · Τ · Α-Τ-Η (F) Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs (In the formula, Η represents a hydrogen atom and other symbols are as defined above); wherein the compound (D) can be obtained by performing an epoxidation reaction between the compound (C) and epihalohydrin. 3. If the phosphorus-containing resin composition in item 1 of the patent application scope further includes: (3) epoxy compounds that do not contain phosphorus. 4. The phosphorus-containing resin composition according to item 3 of the scope of patent application, wherein the content of the epoxy compound containing no phosphorus is 0-95% by weight of the total epoxy compound. 5 · If the phosphorus-containing resin composition in item 3 of the patent application scope includes (4) non-phosphorus hardeners. 6. The phosphorus-containing resin composition according to any one of claims 1 to 5, wherein the ratio of the epoxy equivalent of the epoxy compound to the reactive hydrogen equivalent of the hardener is 0.7: 1 to 1.3: 1. 7. If the scope of the patent application is "Phosphorus-containing hardener in the resin group is the compound of formula (C) as shown in item 2 of the scope of the patent application. 0 This paper size applies to China National Standard (CN S) A4 specification (210 X 297) 5 15726 500761 ____ —__ H3_ 8. For example, the phosphorus-containing resin composition in the scope of patent application No. 5, wherein the content of the phosphorus-free hardener is 0% to 95% by weight of the total hardener. 9. The phosphorus-containing resin composition according to any one of claims 1 to 4 of the patent application scope, further including (5) a hardening accelerator. ^ 1 〇 If the phosphorus-containing resin composition according to item 9 of the patent application scope, wherein the content of the hardening accelerator is 0.01% to 5.0% by weight of the total weight of the composition. 11. The phosphorus-containing resin composition according to item 9 of the scope of the patent application, wherein the hardening accelerator is selected from the group consisting of imidazole compounds, quaternary scale salts, tertiary amines, tertiary phosphines, and quaternary ammonium salts. 1 2. The phosphorus-containing resin composition according to item 1 of the patent application scope, wherein the resin is used for manufacturing a prepreg. I3. The phosphorus-containing resin composition according to item 12 of the patent application scope, wherein a plurality of prepregs made of the resin can be stacked to form a laminated board. 1 4 · The phosphorus-containing resin composition according to item 1 of the patent application scope, wherein the resin can cover a substrate to make a printed circuit board. Printed by the Staff Welfare Committee of the Central Bureau of Standards, Ministry of Economic Affairs This paper is sized to the Chinese National Standard (c N S) A4 (210 X 297 male I) 6 15726