TW448195B - Phosphorus-containing polmer having phenolic units and uses thereof - Google Patents

Abstract

The invention discloses novel compositions of the phosphorus-containing polymer having phenolic units, which include: (1) phosphorus-containing compounds that have at least one epoxy groups and phenolic units, (2) phosphorus-containing hardening agents that have the activated hydrogens which may react with epoxy groups. The invention also discloses the uses of said compositions for prepregs, composite materials, laminators, printed circuit boards and electronic packaging materials. The products obtained from the present compositions have especially excellent processing properties. Moreover, those also have especially excellent flame resistance and high heat resistance without additional flame-resistant agents.

Description

^ 48195 A7 ___ B7 V. Description of the invention (t) Field of invention (Please read the notes on the back before filling in this I ·) This invention relates to a phosphorus-containing epoxy resin composition with a phenolic structure and its use. The product made from this composition has UL94V-0 standard flame resistance and high heat resistance, and does not contain toxic substances such as halogen or antimony trioxide. BACKGROUND OF THE INVENTION Composite materials, especially epoxy materials, have been widely used in coatings, electrical insulation, civil construction materials, adhesives, and laminates due to their simple processability, high safety, superior mechanical and chemical properties. "Field" is especially laminated board made of epoxy resin. Because these resins have strong adhesion to glass fiber cloth and other reinforcing materials, and have no volatile matter and small shrinkage during hardening, the resulting laminated board has a wide range of uses. Excellent mechanical strength, good electrical insulation, good chemical resistance, etc., and can be widely used in electrical and electronic products. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, due to the increasingly sophisticated requirements for the fine wiring and high density of printed circuit boards, laminated boards are also required to have more excellent electrical properties, mechanical properties and heat-resistant processability. At present, the widely used glass transition temperature (Tg) of hardened FR4 multilayer boards is about 130 ° C. Therefore, it is used for cutting and drilling processing of more than 200 ° C in the printed circuit board manufacturing process, and in welding processes above 270 ° C. Easy to crack or burst. Therefore, various laminate materials that emphasize high thermal stability and high glass transition 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 aircraft, automobiles, public transportation and other means of transportation> it is directly related to the safety of life and property, so the flame retardancy of printed circuit boards is absolutely necessary》 This paper standard is applicable to China National Standard (CNS) 2H) X297 mm) 1 15739 4 48? 9 5 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) In order to make the laminated board flame-resistant, it must be introduced to have flame isolation. And reduce the combustion properties of the substance. 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 Strict requirements for characteristics (such as UL94V-0 grade)》 However, if the epoxy resin is to reach the level of UL94V-0, its bromine content must be as high as 17¾ to 21%, and it must be used with antimony trioxide or other flame retardants. Agent. 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 Dioxin compounds, which seriously affect health and the environment. Therefore, the recycling and disposal of the fascia has become a serious problem. As mentioned above, it is urgent to find a new non-combustible material to improve the current environmental pollution caused by laminated boards. Phosphorus compounds printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs have been widely studied and applied as a new generation of flame retardants with environmental protection. For example, use of organic compounds containing red phosphorus or phosphorus (such as triphenyl phosphate, Trityl phosphate, phosphoric acid, etc.) replace halogen compounds as flame retardants to improve the flame retardant properties 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 epoxy resin instead of brominated epoxy resin as a flame retardant substrate has been formulated. For example, U.S. Patent No. 5,37 6,453 uses an epoxy group-containing phosphate ester with a nitrogen-containing ring. Laminated hardener is made of laminated board, but in order to make up for the lack of phosphorus content, it is difficult to reach the standard of UL94V-0 '. Therefore, adding a variety of phosphate esters to epoxidize this paper.

4 4 8 1 9 ： V 881075 A7 B7 Years of the Moon and Moon Amendment Tree 4 I would like to ask if you would like to change the original substance in the future. 5. Description of the invention (3 things: US Patent 5,45 8,97 No. 8 uses epoxy Phosphate esters are combined with nitrogen-containing epoxy resins and metal compounds as hardeners. The glass transition temperature of the finished product is about 1 75 ° C, and the flame retardant properties are only up to UL94V-0 edge (42 seconds vs. critical. 値 50 seconds) and the United States Disclosed in Patent No. 5,506,313. However, none of the above patents have achieved the required difficulty and high heat resistance of 7 kg. The inventors have addressed the shortcomings of the current technology to improve electrical properties, thermal stability, and glass transition temperature Extensive research has been conducted for the purpose, and the present invention has been completed. Detailed inquiry of the invention: It is clear that the present invention relates to a phosphorus-containing epoxy resin composition containing an epoxy group and having a phenolic structure, and its use. Flame-retardant and high heat-resistant prepregs, composite materials, laminates, printed circuit boards, and electronic packaging materials, etc. The present invention discloses a novel phosphorus-containing epoxy resin composition with a phenolic structure, which is characterized by including: : U) Species having a phenol structure and a phosphorus-containing compound containing at least one epoxy group of (A) a resin body: (Read Notes on the back and then fill the page) anthracene-chi Economic Co-op Property Office employee print R '

Formula (A) where 'm + n = 3 to 20, m = l to 15, p = 0-10, X = 〇 or electron pair, τ = 〇 or electron pair, 3 (correction page) 15739 paper size Applicable to the Chinese national standard (⑽) Cong Mi (21〇χ297 公 ⑹ A7 B7

Rb

V. Description of the invention (Y-

Rb = NH2, OH, CrC10 R ^ R'Ci-Cufluorenyl, aryl or aralkyl

Ra = H, CH3, CH2 = CH (Please read the precautions on the back before filling this page)

Ri, R2 = H, CVC2. Alkyl, (^ T -2 (0T • CH < ^ _ ^ C (G {3) 2 ^ C (Gi; j) 2 r

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R, T x = i Winter ET [0 R3, R4 = H, CrC4 alkyl; (2) —A hardener with active hydrogen that can react with epoxy groups. In addition, the present invention also discloses a novel epoxy-containing phosphorus-containing resin composition, which specifically includes: (1) an epoxy compound containing at least one epoxy group (2)-a phenolic structure and at least A hydroxyl-containing phosphorus hardener (B):

Ra! -FY—CH-Λ Formula (B) The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 4 (Repair IEK) 15739 A7 B7 V. Description of the invention (5) In the formula, m + n = 3 to 20, m = l to 15 'P = 〇_l〇X = 0 or electron pair, T = 0 or electron pair,

Rb Υ- NH— nWn-

—C = 0, © Ί

Rb = NH2, OH, CVC10 alkyl R’.R'CVCh alkyl 'aryl or aralkyl'

Ra = H, CH3 'CH2 = CH' © Cr © " HO-0 · (Please read the precautions on the back before filling this page)

Rt. R2 = h '〇! -〇20 m r

C (C?: 3) 2-Printed by R3 of the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs. R4 = h, cvc4 alkyl "Furthermore, the present invention also discloses a novel phosphorous epoxy resin composition, which is composed of A combination of a phosphorus-containing compound (A) containing an epoxy group and a phenolic structure and a phosphorus-containing hardener (B) having a phenolic structure and a hydroxyl group. The preparation of the phosphorus-containing compound containing at least one epoxy group and having a phenolic structure (sometimes also referred to herein as a phosphorus-containing epoxy resin having a phenolic structure) used in the resin composition of the present invention is prepared by directly using epihalohydrin The compound represented by formula (B) is obtained by epoxidation. The epihalohydrin used such as epichlorohydrin and epibromopropane " The phosphorus-containing compound disclosed in the present invention which contains at least one epoxy group and has a phenolic structure can also be used in accordance with conventional methods, without using halides In this case, with silicon reinforced material, after mixing and crushing and ingot making electronic package. The paper size is applicable to China National Standard (CNS) A4 specification (210 x 297 mm) 5 (repair) 15739

Order ---------- line. V A7 B7 V. Description of the invention (6) (锖 Read the precautions on the back before filling in this page) Materials, and then hot-pressed to obtain environmentally-friendly electronics Package. The electronic package has flame retardant effect, thermal stability, dimensional stability and electrical properties that meet and even far exceed current product standards. It is suitable for manufacturing electronic products in space, transportation, etc., and for printing Circuit boards and multilayer circuit boards. The phosphorus-containing hardener (B) having a phenolic structure and containing at least one hydroxyl group used in the resin composition of the present invention is obtained by reacting a phosphorus-chlorine functional compound (C) with a phenolic resin:

X

_. CL-P-T-Ri ·· · I τ Formula (c)

I R'l Member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperative Printing (where X is an oxygen or electron pair, T is an oxygen or electron pair, R〆, R2 ”may be C ^ -Cm alkyl or alkenyl , Aryl, alkenyl-substituted aryl, etc., Ci-G alkyl, C, C4 alkenyl, phenyl, naphthyl, biphenyl, phenyl ether, benzene substituted with 1 or 2 CrC4 alkyl Phenyl or naphthyl is preferred). All polyphenolic phenolic waxes can be used in this reaction to obtain the phosphorus-containing hardener (B) with a phenolic structure and containing at least one hydroxyl group required by the present invention. The phenolic resin is preferably, for example, phenolic resin, cresol novolac resin, xylenol novolac resin, phenol novolac resin, isobutylphenol novolac resin, nonylphenol novolac resin, bisphenol A phenolic resin, bisphenol F phenolic resin, biphenol Phenol novolac resin, melamine phenolic resin, etc. In addition, other polyphenols can also be used in this reaction to prepare compounds of formula (B), such as

6 (修 ΙΕΜ) 15739 This paper size is applicable to China Store Standard (CNS) A4 (210 X 297 mm) 4 4 β? 9 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 _______ Β7_ V. Description of Invention (7) 2 = 1 to 100, and the phosphorus-chlorine-containing compound used in the above reaction, if

X

II Contains other types of phosphorus-chlorine compounds, such as ci2-p-t-r ’, but the main product obtained is a compound of formula (B), but it will also generate a phosphorus-containing resin with the following structure and having an aldehyde structure:

X

II P-T-R ’

0H 0

(In the formula, the symbols are defined as described above), but the existence of such compounds does not affect the properties of the composition of the present invention, and the reaction product can still be directly used in the formulation of the present invention. The phosphorus-containing hardener (B) obtained by the above reaction may be used alone or in combination with other phosphorus-containing or non-phosphorus-containing hardeners. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page}

15739 4 48 I 9. A7 _B7_ V. Description of the invention (8) In addition to the above components, the resin composition of the present invention may be blended with other conventional epoxy compounds as required to meet operational requirements and to achieve the cost of the composition of the invention. Final properties required for the finished product. The epoxy compound used in the present invention means an epoxy compound containing or not containing phosphorus, and preferred examples thereof include, for example, bisphenol (phenol), phenol, hydroquinone, biphenol, hydrogen, and alkane Glycidyl ether, glycidyl amine, glycidyl thioether, and glycidyl amine, olefins, cyclic hydrocarbons, nitrogen-containing heterocycles, phenols, siloxanes, polysiloxanes, and the like Glycidyl carbonyl ester and the like. The diglycidyl ether of bisphenol may be -Ph-Y-Ph- (in this group, Y represents -CH2-, -C (CH3) 2-, -CH (CH3)-, -0-, -S -, -C (0)-, -S02-, etc.), examples of which include bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, tetramethylbis Phenol A glycidyl ether, tetramethylbisphenol F glycidyl ether, tetramethylbisphenol AD glycidyl ether, tetramethylbisphenol S glycidyl ether, and the like. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Examples of glycidyl ethers of biphenol include 'for example 4,4'-biphenol glycidyl ether, 3,3'-di Methyl-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 'e.g. resorcinol glycidyl ether, hydroquinone glycidyl ether, isobutyl hydroquinone glycidyl ether, and the like. Examples of the polyglycidyl ether of novolac include 'e.g. polyaldehyde glycidyl ether, cresol novolac polyglycidyl ether, bisphenol A novolac polyglycidyl ether, and the like. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 8 15739 ^ 4 '8 IS i A7 B7 V. Description of the invention (9) (Please read the notes on the back before filling this page) Other polyphenols Examples of polyglycidyl ethers include, for example, ginseng (4-hydroxyphenyl) methane polyglycidyl ether, ginseng (4-hydroxyphenyl) ethane polyglycidyl ether 'ginseng (4-hydroxyphenyl) glycerol polyglycidyl Glyceryl ether, ginseng (4-hydroxyphenyl) butane polyglycidyl ether, ginseng (3-methyl-4-hydroxyphenyl) methane polyglycidyl ether, ginseng (3,5-dimethyl-4-hydroxyl) Phenyl) methane polyglycidyl ether, methyl (4-hydroxyphenyl) ethane polyglycidyl ether, methyl (3,5-dimethyl-4-hydroxyphenyl) ethane poly @ water glyceryl ether, etc. Mixtures of the various glycidyl ethers described above may also be used. Among the above glycidyl ethers, preferred are bisphenol A polyglycidyl ether having a bifunctional group, resorcinol glycidyl ether, and the like, and a trifunctional ginseng (4-hydroxyphenyl) methane polycondensation Glyceryl ether, etc., compounds with tetrafunctional (4-hydroxyphenyl) ethane polyglycidyl ether, cresol novolac polyglycidyl ether, or mixtures thereof "and > Examples of other epoxy compounds are, for example, Various epoxy compounds obtained by the direct oxidation of hydrogen peroxide with compounds having a double bond structure, including dicyclopentadiene epoxide,

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Epoxides of styrene derivatives and epoxy compounds of cycloolefins can also be used in the composition of the present invention. In addition to the above components, the resin composition of the present invention may be used in combination with a conventional phosphorus-free hardener as required, depending on the final properties required of the composition. The term “phosphorus-free hardener” as used in the present invention includes, for example, those containing a Chinese paper standard (CNS) A4 (210X 297 mm) that can be applied to the paper size of the paper. 9 15739 Α7 B7 5. Description of the invention (10) Oxygen reaction Examples of active group compounds are, for example, amines, bisphenols, benzodiazepines 'polyfluorenes, carboxaldehydes, naphthalenes, naphthenes, cyclic hydrocarbons' nitrogen-containing heterocyclic rings, siloxanes, polysiloxanes, polysiloxanes Thiols, polycarboxylic acids and the like or mixtures thereof. Examples of suitable amines include ' e.g. Dicyandiamide, diaminodiphenylmethane, and the like. Examples of suitable polyphenols include, for example, ginseng (4-hydroxyphenyl) methane, ginseng (4-hydroxyphenyl) ethane, ginseng (4-hydroxyphenyl) propane 'ginseng (4-hydroxyphenyl) butane, Ginseng (3-methyl-4-hydroxyphenyl) methane, ginseng (3,5_diamidino-4-hydroxyphenyl'yl) methane, (4-hydroxyphenyl) ethane, (3,5 -Dimethyl-4-hydroxyphenyl) ethane and the like. Examples of suitable novolacs include, for example, phenol-formaldehyde condensates, cresol novolac condensates, bisphenol A novolac condensates, and melamine-phenol novolac condensates. The amount of the hardener added depends on the reactive hydrogen equivalent of each hardener and the epoxy equivalent of the epoxy resin, but generally, the reactive hydrogen equivalent of the hardener is usually 100% relative to the epoxy equivalent of the epoxy resin. 10 to 100%, more preferably 50 to 90% »The resin composition of the present invention can be applied to applications in the field of high heat-resistant materials, such as laminates, integrated circuit board packaging materials, electronic packaging materials, and high heat-resistant powder coatings. Packaging, engineering plastics, etc. > Hardening accelerators, solvents, catalysts and other additives can also be added to the resin composition of the present invention as needed. The hardening accelerators used in the present invention are, for example, tertiary amines, tertiary phosphines, quaternary ammonium salts, quaternary phosphonium salts, and imidazole compounds. These hardening accelerators can be used singly or in combination of two or more types. "This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)- --Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 (correction page) 15739 4 481 95 Α7 Β7 i. Description of the invention (U) The tertiary amine includes, for example, triethyl Methylamine, tributylamine, dimethylamine ethanol, ginseng (N, N-dimethylaminomethyl) phenol, N, N-dimethylaminocresol and the like. (Please read the notes on the back before filling out this page.) Tertiary phosphines include, for example, triphenylphosphine. Quaternary ammonium salts include, for example, tetramethylammonium chloride, tetramethylammonium bromide, citromethylammonium iodide, triethylbenzyl ammonium chloride, triethylbenzyl ammonium bromide, triethyl iodide Benzyl ammonium, etc. Quaternary scale salts include, for example, tetrabutylscale chloride, tetrabutylphosphonium bromide, tetrabutylscale iodide, tetrabutylrust acetic acid complex, tetraphenylscale chloride 'tetraphenyl iron bromide, iodine Tetraphenyl scale 'Ethyl triphenyl chloride scale, ethyl triphenyl scale bromide, ethyl triphenyl scale iodide, ethyl triphenyl iron acetate complex' ethyl triphenyl scale Phosphate complex, propyl triphenyl chloride scale, propyl triphenyl bromide scale, propyl triphenyl iodide scale, butyl triphenyl chloride, 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 hardening accelerators printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are imidazole compounds and quaternary phosphonium salts, especially 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonic acid complex, and bromination Butyltriphenyl iron is 隹 β. The above hardener accelerators can be used alone or in combination of two or more. The amount of the hardening accelerator is preferably 0.00 5 to 5.0% by weight based on the total weight of the composition, preferably 0.05 to 4.5% by weight, more preferably 0.1 to 4.0% by weight, and most preferably 0.15 to 3.0% by weight »If Adding an excessive amount of hardening accelerator can shorten the reaction time, but it is easy to produce this paper. The size of the paper is applicable to the Chinese National Standard (CNS) Α4 size U 丨 mm} 11 15739 4 48 · 1ί 35 Α7 Β7 5. Description of the invention (12) {Please first (Please read the notes on the back and then fill out this page). By-products have an adverse effect on the applicability of a. For example, when it is used for the substrate of a circuit board, 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 to be conducive to industrial use. In the composition of the present invention, the viscosity of the composition can also be adjusted by adding a solvent. 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 ( Brookfiel® 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, propane, methyl ethyl ketone, and methyl isobutyl ketone. Protic solvents include, for example, N, N-dimethylformamide, N, N-diethylformamide, dimethylmethylene ether, and ethers include, for example, ethylene glycol monomethyl ether and propylene glycol monomethyl ether. The esters include, for example, ethyl acetate, ethyl isopropylate. The catalyst used in the composition of the present invention may be, for example, a 10% triphenylphosphine methanol solution (catalyst A). Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. 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 laminates, electronic packaging materials, high-heat-resistant powder coating, and the like. The resin composition of the present invention can also be prepared by impregnating a substrate by an impregnation method. Impregnated substrates can use organic or inorganic materials such as paper, glass paper. Applicable to China National Standard (CNS) A4 specifications (210 × 297 mm) 12 15739 4 48 Α7 B7 V. Description of the invention (13) Glass, metal, Carbon fiber, boron fiber, cellophane and organic polymers. (Please read the precautions on the back before filling this page) The resin composition of the present invention can be made into a laminated body including copper foil, fiber support and resin composition of the present invention according to conventional methods. 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 alone as an adhesive layer for prepreg, or after one or more prepregs are combined, copper can be placed on one or both surfaces. After the foil is heated with pressure, a laminated board is obtained. The dimensional stability, chemical resistance, corrosion resistance, moisture absorption and electrical properties of the obtained laminated board are far superior to the current product standards. It is suitable for the manufacture of electrical products such as electronics, space and transportation, and for manufacturing Printed circuit boards and multilayer circuit boards, etc. "The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the phosphorus-containing compounds shown in the present invention that contain at least one epoxy group and have a phenolic structure. In this case, with silicon reinforcing material, after mixing, pulverizing, and ingot making into electronic packaging materials, and then hot-press molding to obtain environmentally friendly electronic packages. The electronic package has flame retardant effects, thermal stability properties, dimensional stability, and electrical properties that meet and even far exceed current product standards, and is suitable for use in the manufacture of electronic products for electronics, space, transportation, etc., and for manufacturing Printed circuit boards and multilayer circuit boards. The phosphorus-containing compound containing at least one epoxy group and having a phenolic structure disclosed in the present invention can also be made by mixing, pulverizing, and ingot-making with a silicon reinforcing material without using a halide according to a conventional method. Electronic packaging This paper is in accordance with China National Standard (CNS) A4 specification (210 × 297 mm) 13 15739 4 4 81 So A7 B7 V. Description of the invention (i4) The material is then hot-pressed to obtain an electronic package that meets environmental protection conditions . The electronic package has flame retardant effects, thermal stability, dimensional stability and electrical properties that meet and even far exceed current product standards. It is suitable for manufacturing electronic products for electronics, space, transportation, etc., and for printing Circuit boards and multilayer circuit boards. In summary, the present invention provides an excellent flame resistance, thermal stability and mechanical properties; ^ a novel epoxy-containing phosphorus-containing resin composition with a phenolic structure and its use "The present invention will be described in detail by the following examples, but These examples are only used to illustrate the present invention, but 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 (EEW, Epoxy Equivalent Weight): The epoxy resin is dissolved in chlorobenzene: chloroform = 1: 1 solvent, and HBr / glacial acetic acid is used. Titration was performed according to the method of AS TM D 1 652, wherein the indicator was crystal violet. Solid content: The weight percentage of non-volatile matter measured by taking a varnish sample of an epoxy resin composition and drying it at 150 ° C for 60 minutes. The types of epoxy resin used in the following are as follows: Phenolic resin A: A phenolic condensate produced by Changchun Artificial Resin Factory and sold under the trade name PF5110. Its hydroxyl equivalent is 108 g / eQ. Phenolic resin B: a phenolic condensate produced by Changchun Artificial Resin Factory and sold under the trade name HOCN200B. Its hydroxyl equivalent is 120 g / eq. Phenolic resin C: a phenolic condensate produced by Changchun Artificial Resin Factory and sold under the trade name BN7135. Its hydroxyl equivalent is 124 g / eq. Epoxy Resin 1: Produced by Changchun Man-made Resin Factory, under the trade name (please read the precautions on the back before filling this page). Order printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs. This paper applies Chinese national standards (CNS) Specification of 8.4 (210X297 mm) 14 15739 448ί 9 'Α7 Β7 5. Description of the invention (15) The diglycidyl ether of bisphenol A sold by BE 188EL has an epoxy equivalent between 185 and 195 g / eq. Hydrolyzed chlorine is less than 200 ppm and viscosity is between 1 1,000 and 15,000 cps / 25 ° C. Epoxy resin 2: Tetrabromobisphenol A diglycidyl ether produced by Changchun Artificial Resin Factory and sold under the trade name BEB530A80. Its epoxy equivalent is between 430 and 450 g / eq, and the bromine content is between 18.5 and 20.5% by weight. Epoxy Resin 3: Produced by Changchun Artificial Resin Factory * Tetrabromobisphenol A diglycidyl ether sold under the trade name BEB5 26A 80. Its epoxy equivalent is between 410 and 43 Og / eQ. Between 19.0 and 21.0% by weight. Epoxy resin .. Grease .. 4: An epoxy resin produced by Changchun Artificial Resin Factory and sold under the trade name CNE-200. Its epoxy equivalent is about 200g / eQ. Hardener A represents a 10% solution of dicyandiamide in DMF. Catalyst A represents a 10% solution of triphenylphosphine in methanol. The hardening accelerator represents a 10% solution of 2-methylimidazole in DMF. Synthesis Example 1: Synthesis of Phosphorous Resin A with Phenolic Structure

A three-liter five-necked flask was used as a reaction vessel. The flask was equipped with a device for controlling and displaying temperature and pressure. 615 g of phosphorochlorine (POCl3) and 5.4 g of anhydrous magnesium chloride were added thereto, and the temperature was raised to 100 ° C. And at a certain rate, 750 g of phenol was added within 2 hours, and the reaction was continued for 2 hours after the addition was completed. Then, at the same temperature, 600 g of phenolic resin A (108 g / eq of OH equivalent) was added and the reaction was continued for 2 hours. Then, 1,000 g of methyl ethyl hydrazone was added, and after washing three times with distilled water, the solvent was distilled off under reduced pressure. To get 1 670 grams of light yellow I (Please read the precautions on the back before filling this page)

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, the paper size applies to Chinese National Standards (CNS) Α4 ^ grid (2 ×× 297 mm) 15 15739 A7 B7 V. Description of the invention (16) Phosphorous resin A with phenolic structure, its OH equivalent It is 442 g / eq. Synthesis Example 2: Synthesis of Phosphorous Resin B with Phenolic Structure Except for the use of cresol-phenolic resin (phenolic resin B, whose 0H equivalent is 120g / ec0 phenolic resin A, the rest are the same as in Synthesis Example 1, And the phosphorus resin B with phenolic structure was obtained, and its 0H equivalent was 460 g / et5) = Synthesis Example 3: Synthesis of phosphorus resin C with phenolic structure except that bisphenol A-phenolic resin (phenolic resin C, 0H The equivalent was 120 g / eq) except that the phenolic resin A was replaced, the rest were the same as those in Synthesis Example 1, and a phosphorus-containing resin C having a phenolic structure was obtained, and its 0H equivalent was 482 g / eQ. The following Synthesis Example 4-5 was used to synthesize a phosphorus-containing resin having an epoxy group and a formaldehyde structure: Synthesis Example 4: Synthesis of a phosphorus-containing epoxy resin D having a phenolic structure A 3-liter five-necked flask was used as a reaction vessel. Equipped with a device for controlling and displaying temperature and pressure, and a device for condensing and separating the common mixture of water and epoxy halopropane. 700 g of a phosphorus-containing resin with a phenolic structure prepared in Synthesis Example 1 was added to the flask. A and 880 grams of epichlorohydrin. The resulting mixture was stirred at atmospheric pressure until uniformly dissolved, and then heated to 70 ° C under an absolute pressure of 19 mmHg, and at a constant rate and pressure at a rate of about four 154.7 grams of a 49.3% sodium hydroxide solution was added within hours. After the reaction was completed, the remaining epichlorohydrin and the solvent were distilled off under reduced pressure. The obtained epoxy resin was dissolved in a solution of methyl ethyl ketone and deionized water. The sodium chloride in the resin was washed with water, and then methyl ethyl ketone was distilled off under reduced pressure, to obtain 7 80 g of light brown phenolic structure yose phosphate resin A with an epoxy equivalent of 468 g / eq »(please first (Read the notes on the back and fill out this page) • 1.- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 (2I × 297mm) 16 15739 Α7 Β7 V. Description of the invention (17) Synthesis example 5: Phenolic Synthesis of structured phosphorus-containing epoxy resin B (please read the precautions on the back before filling this page) Except using the ortho-containing resin B prepared in Synthesis Example 2 instead of the phosphorus-containing resin A with phenolic structure The rest are the same as those in Synthesis Example 4, and a salvianol structure-containing phosphorus epoxy epoxy resin B having an epoxy equivalent weight of 490 g / eq is obtained. The epoxy resin composition of the present invention is shown in Table 1 in Examples. 1-6. Comparative Examples 1 and 2 are the control group. At room temperature, the phosphorus-containing epoxy resin, the hardening agent, the hardening accelerator, and the solvent synthesized above are shown in Table 1 in a container equipped with a stirrer and a condenser. The addition ratio shown is adjusted to form a phosphorus-containing epoxy resin composition: Table 1 Composition formulas of each example and comparative example Composition composition Formula ⑻ Implementation: mi suspect 1: Implementation: Example reading Example 4 Implementation: Example 孓Example_6: Comparison :: Ml: Comparative Example i Synthetic Example 4 180 Synthetic Example 5¾ Containing Facial B 180 180 Viewer r-160 140 100 150 Epoxy Resin 2 125 Lai Resin 3 40 125 mm 200 240 Synthetic Example 2: Contains _Purpose 3 (::: 190 190 210 Hard Pour! ΊΑ 40 180 15 250 260 雠 A Triphenyl Hall's armor fiber Τ: :: 1 1 1 1 1 1 10% 2-A__ DMF _ 0.625 0.625 The printed property test of the Employee Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs will The glass fiber cloth was impregnated with the phosphorus-containing epoxy resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 2, and dried at 150 ° C to become a prepreg, and then DSC (scanning calorimeter, TA2910) (differential 15739 This paper size applies to Chinese national standard {CNS) A4 specification {210X297 mm) δ 4 4 6 9 A7 V. Description of the invention (18) scanning calorimeter (TA29 10) Test the glass transition temperature for thermogravimetric analysis The method (TGA) measures its heat loss and tests its flame retardancy by a fire test. The results are shown in Table 2. From Table 2, it can be seen that the prepreg made of the composition of the present invention has flame retardancy and its thermal weight. Loss temperature and glass transition temperature also increase A lot. Table 2 Flame retardancy and thermal stability of prepreg after baking at 180 ° C for 120 minutes (please read the precautions on the back before filling this page) and the glass transition temperature;. ;;;; Example 1 Implementation— Implementation: Binsch mm ::: 窭 施 :: Implementation. Mm 雠 :::: Comparative example 2: 2 :: .. Combustion test * 'Pass pass pass pass pass Mm pass 1: Xiangu check quiet || 1 丨:: 305 312 310 330 303 301 250 250 Tg (0C). 189 194 192 187 188 193 132 150 Note: * flame test: According to UL94V-0 method. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed eight pieces of the above-mentioned various prepregs respectively, and placed a piece of 35 micron copper foil on top and bottom, and pressed at a temperature of 185 ° C and a pressure of 25 kg / cm2 to obtain the pre- The detailed analysis results of the laminated body of immersion and glass fiber cloth are shown in Table 3. From the table, it can be known that various test items of the laminated body made of the composition of the present invention can meet the required standards, as shown in Table 3. Table 3 Test results of the physical properties of the substrate after heating and pressing: analysis item :: heading: piece, and heart window. Grid .: Example 1 Example 2 Example: 6. Comparative Example 2 Resistance to soldering: Property IPC260 ° C specifications > 10 Pass and pass, peel strength IPC i > 8 lb / in 8.50 8.70 8.70 8.90 surface resistance IPC specifications > 1012 2.57 * 1015 2.25 * 1015 4.56 * 1015 3.57 * 1015 bulk resistance IPC specifications > 1010 1.08 * 1014 9.56 * 1013 1.87 * 10i4 ι.οβηο14 Positive dielectric constant (: Specifications < 5.4 4.5 4.6 4.6 4.6 Diffusion factor — 0.018 0.020 0.018 0.020 Tg (° C) DSC 190 203 210 Π 153 Size of this paper Applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 18 15739 A7 B7 V. Description of the invention (19) In summary, it can be known that the prepreg made of the composition of the present invention and its laminate are particularly flame-resistant The glass transition temperature is better, at least 19 (TC or even up to 200 ° C or higher, the solder resistance of the finished product 1 peel strength, surface resistance, bulk resistance, dielectric constant and dissipation factor, etc. also meet the required specifications Even better. The phosphorus-containing epoxy resin composition of the present invention According to the formula shown in Table 4 below, they were formulated into the packaging materials of Example 7 and Example 8. Comparative Example 3 and Comparative Example 4 are for comparison. The various ingredients of each formula are evenly combined and crushed. After the double-roller kneading machine is mixed, it is crushed and ingot to obtain the packaging material. The two packaging materials are tested for molding and properties, and the results are shown in Table 5. (Please read the precautions on the back before filling in this tile) Economy Printed by the Intellectual Property Bureau of the Ministry of Intellectual Property and Consumer Cooperatives. 4 Formulation composition of packaging materials containing tritium | _ 议 __ ^ | ^ ___ | i 面面 _. Example 8: Ma ____ Comparative Example 4- 540-790 790 Noodles,-620--Ning_Mission: __ | _ || Negotiations--3 650-"--400 400 400 Stone 2800 2800 2800 2800 5.2 5.2 5.2 5.2 Cut courtyard 14.2 14.2 14.2 14.2 iwt m ^ k: 7.2 7.2 72 7.2 JJSC .... m- 11 11 11 11 Antimony trioxide ^---7.2 This paper size applies to Chinese National Standard (CNS) A4 specification (210X2W mm) 19 15739 81 A7 ______B7 V. Description of the invention ( 2Q) Property test of the material containing P # after molding

Item Condition Example 7 Example 8 Comparative Example 3 Comparative Example 4 Melt viscosity 175. . 50 poise 52 poise 79 poise 83 poise Gelation: time 160. . 28 seconds 27 seconds 28 seconds 29 seconds Difficult. Bet: Sex UL 94V-0 Passed Passed Passed :: Degrees of Centimeter ”68 cm 59 cm ^ 55 cm Miscellaneous P Transfer Temperature DSC 165〇C 167〇C 160 ° C 163 ° C It can be seen from Table 5 that the packaging materials prepared with the composition of the present invention are superior to the comparative examples in terms of melt viscosity, gelation time, flame retardancy, fluidity, and glass transition temperature after molding. (谙 Please read the notes on the back before you fill out this page) Order-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm) 15739 20

Claims (1)

Ra = H 'CH,' CH, = CH H3 No. 8 8 1 〇 7 5 6 8 Patent Application Amendment of Patent Scope (A phosphorus-containing epoxy resin composition with a phenolic structure on February 15, 1990, Including: (1) Phosphorous compounds (A) containing one or more epoxy groups and having a bismuth aldehyde structure: Rr I 0 T CGi.GKH, xi-T-R'- Formula (A) In the formula, m + n = 3 to 20, m = l to 15 ·, · ρ = 1-10 χ = 0 or electron pair, T = ◦ or electron pair, ΝΉ- Rb Rb 0 ° ^ _C = 0, ◎ Rb = NH2, OH ,. Alkyl 〇ύ This paper size applies to China National Standard (CNS) A4 specification (210X 297 public love) 15739 € 4β195 Η3 R! H c "c2. Alkyl, a 'bd ^. 〇09 R3, R4 = H, CrC4 alkyl; (2) A hardener with active hydrogen capable of reacting with epoxy groups, including: U) Phosphorus-free hardener, selected from amines, bisphenols, resorcinols, polyphenols, phenolics, naphthalene ' Compounds such as olefins, cyclic hydrocarbons, nitrogen-containing heterocycles' siloxanes, polysiloxanes, polythiols, and polycarboxylic acids, or mixtures thereof; or (b) phosphorus-containing hardeners, which have a phenolic structure and contain Compounds with one or more hydroxyl groups, where the phenolic structure is a phenol ... aldehyde resin; the amount of the above-mentioned hardener added to the epoxy equivalent of the epoxy resin is 100%, and the reactive hydrogen equivalent of the hardener is 10 to 1 0 0%. A phosphorus-containing epoxy resin composition, including: Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs (1) An epoxy compound containing one or more epoxy groups, which is a phosphorus-containing or phosphorus-free epoxy compound An epoxy compound selected from bisphenol, phenol, benzenedifluorene, biphenol, naphthalene, Hydrocarbons, olefins, cyclic hydrocarbons, nitrogen-containing heterocycles, phenols, siloxanes, polyglycidyl ethers, glycidylamines, glycidyl sulfide, and glycidyl carboxylic acid esters; (2) Has Phosphorus-containing hardening agent (B) with phenolic structure and containing one or more hydroxyl groups: This paper is also applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 public change) T5TJV 9 Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs 4 4 H3 GE Χί Χ =? Ϋ Ra-(-Υ—CH-) = 'Rl Ri cl St Formula (B) where' m + n = 3 to 20, m = 1 to 15, p = 0- 10 X = 〇 or electron pair, T = 0 or electron pair, iMH '" * " · 1 ^ rdr ° ~ 0 = 0 Rb = NH2, OH, CL-CL0 alkyl, ◎' Ο R ', R "= C" C1S alkyl' aryl or aralkyl Ra = H 'CH, CH, = CH' -Οΐ ^ h, r2 = h, c "c2. Alkyl, 10 ^, ί ^ Γ〇 [〇Γ BD R3, R4 = H, CrG alkyl; CHr ^ -CCCH3) 2- no *. -CCGi]) 2 The amount of the above-mentioned hardener added to the epoxy equivalent of the epoxy resin is 100%, and the hydroxyl equivalent of the hardener is 10 to 100%. For example, the phosphorus-containing epoxy resin composition in the scope of the patent application, wherein (2) the hardener is dicyandiamine-diaminodiphenylmethane, phenol formaldehyde-phenol resin, cresol formaldehyde-phenol resin, Bisphenol A formaldehyde-phenolic resin, dicyclopentadiene phenol resin, dicyclopentadiene cresol resin, naphthol This paper size is applicable to China National Standard (CNS) A4 specification (210 parent 297 male cage) 3 15739 4481 9t H3 resin, phenylenediamine, phthalic anhydride, melamine-phenol-phenolic condensate, bisphenol F, bisphenol S, or formaldehyde-phenolic resin, and mixtures thereof. 4. For example, the phosphorus-containing epoxy resin composition in the scope of the patent application, wherein (2) the amount of the hardener added is 50 to 90¾ based on 100% of the epoxy equivalent of the epoxy resin. 5. For example, the phosphorus-containing epoxy resin composition of the scope of the patent application, wherein (2) the amount of the hardener added is 50 to 90% based on the epoxy equivalent of the epoxy resin. 6. For example, the phosphorus-containing epoxy resin composition in the scope of patent application, the hardener of component (2) is the one containing the phosphorus-containing hardener (B) in scope of the patent application. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs 7. If the phosphorus-containing epoxy resin composition in the scope of patent application item 1 further includes: (3) phosphorus-containing epoxy compounds other than formula (A) and / or other Phosphorus-containing epoxy compounds, which are selected from the group of bisphenols, phenols, hydroquinones, biphenols, naphthalenes, alkanes, alkenes, cyclic hydrocarbons, nitrogen-containing heterocycles, phenols, siloxanes, and polysiloxanes. Glyceryl ether, glycidylamine, glycidyl sulfide, and glycidyl carboxylic acid esters: wherein the content of phosphorus-containing epoxy compounds and / or other phosphorus-free epoxy compounds other than the formula (A) is cyclic The total amount of oxygen compounds is 1 to 99% by weight. 8. If the phosphorus-containing epoxy resin composition in item 2 of the patent application scope further includes: (4) other phosphorus-containing hardeners and / or phosphorus-free hardeners other than formula (B), are selected from Amines, bisphenols, hydroquinones, polyphenols, phenols, naphthalenes, olefins, cyclic hydrocarbons, nitrogen-containing heterocycles, siloxanes, polysiloxanes, polythiols, and polycarboxylic acids or have phenolic structures And compounds containing one or more hydroxyl groups; among which, the paper sizes other than g I: B) apply to China National Cotton Standard (CNS) A4 (210 X 297 male cage) 4 15739 t4.S l 95 H3 containing The content of the dish hardener and / or no ortho hardener is 1 to 99% by weight of the total hardener. 9. If the phosphorus-containing epoxy resin composition in the scope of patent application item 1 or 2 includes hardening accelerators. 10. For example, the phosphorus-containing epoxy resin composition according to item 9 of the application, wherein the proportion of the hardening accelerator is from 0.01% to 5.0% by weight of the total weight of the composition. 11. For example, the phosphorus-containing epoxy resin composition according to item 9 of the application, wherein the hardening accelerator is an imidazole compound, a quaternary scale salt, a tertiary amine 'tertiary phosphine, or a quaternary ammonium salt. 12. For example, the phosphorus-containing epoxy resin composition in the scope of patent application No. 1 or 2 is used to prepare films. 1 3 ^ The phosphorus-containing epoxy resin composition according to item 1 or 2 of the scope of patent application is used to prepare a high heat-resistant laminated board without halogen. Printed by the Central Welfare Committee of the Ministry of Economic Affairs. Lipid composition tree fat oxygen. Tree installation Ring plate oxygen seal Phosphorus road ring property Brush with dish heat Containing high resistance to printing 2 Highest of 2 items? Vegetarian or halogen or halogen 1 containing 1 containing non-reserved and non-reserved systems and norms 范 ΓΠ and U are also used for special purpose, please apply for the application, please apply for the application. The paper size applies Chinese national standards (CNS) A4 specification (210X297 public reply) 15739 5 4 4 8 1 9: V 881075 A7 B7 Years and months amend the tree 4 I would like to ask if you would like to change the original substance after the five. Description of the invention (3 things: US patent 5,45 8,97 No. 8 uses epoxy phosphate with nitrogen-containing epoxy resin and metal compounds as hardeners. Its finished glass transition temperature is about 1 75 ° C, and its flame resistance is only up to UL94V-0 edge ( 42 seconds is critical. 値 50 seconds) and disclosed in US Patent No. 5,506,313. However, none of the above patents has achieved the required difficulty and high heat resistance of 7 kg. The present inventors have addressed the shortcomings of the current technology in order to Extensive research aimed at improving electrical properties, thermal stability, and glass transition temperature has led to the completion of the present invention. Detailed inquiry of the invention: The present invention relates to a phosphorus-containing epoxy resin composition containing an epoxy group and a phenolic structure. And its use By using this composition, prepregs, composite materials, laminates, printed circuit boards, and electronic packaging materials with flame resistance and high heat resistance can be prepared. The present invention discloses a novel phosphorus containing phenolic structure The epoxy resin composition is characterized by: U) —A phosphorus-containing compound (A) with a phenolic structure and containing at least one epoxy group as the resin body: (Please read the precautions on the back before filling this page) Economy Printed on R 'by the Consumer Cooperative of the Ministry of Intellectual Property Bureau Formula (A) where 'm + n = 3 to 20, m = l to 15, p = 0-10, X = 〇 or electron pair, τ = 〇 or electron pair, 3 (correction page) 15739 paper size Applicable to the Chinese National Lu Zhun (⑽) Cong Mi (21〇χ297 公 ⑹ Ra = H 'CH,' CH, = CH H3 No. 8 8 1 〇 7 5 6 8 Patent Application Amendment of Patent Scope (A phosphorus-containing epoxy resin composition with a phenolic structure on February 15, 1990, Including: (1) Phosphorous compounds (A) containing one or more epoxy groups and having a bismuth aldehyde structure: Rr I 0 T CGi.GKH, xi-T-R'- Formula (A) In the formula, m + n = 3 to 20, m = l to 15 ·, · ρ = 1-10 χ = 0 or electron pair, T = ◦ or electron pair, ΝΉ- Rb Rb 0 ° ^ _C = 0, ◎ Rb = NH2, OH ,. Alkyl 〇ύ This paper size applies to China National Standard (CNS) A4 specification (210X 297 public love) 15739