US 20020032279A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2002/0032279 A1 Hwang et al. (43) Pub. Date: Mar. 14, 2002

(54) FLAME RETARDANT RESIN AND FLAME Publication Classification RETARDANT COMPOSITION CONTAINING

THE SAME (51) Int. Cl." ...... C08F 8/00 (52) U.S. Cl...... 525/107 (75) Inventors: Kuen Yuan Hwang, Hsinchu (TW); Hong-Hsing Chen, Hsinchu (TW); An (57) ABSTRACT Pang Tu, Hsinchu (TW); Huan-Chang The present invention relates to a phosphorus-containing Chao, Hsinchu (TW) epoxy resin, which is an epoxy resin modified with a side Correspondence Address: chain having a reactive phosphorus-containing compound. EDWARDS & ANGELL, LLP Also, the present invention relates to a flame-retardant resin Dike, Bronstein, Roberts & Cushman, IP Group composition, which comprises: 130 Water Street (1) the phosphorus-containing epoxy resin, Boston, MA 02109 (US) (2) a halogen-free hardener having a reactive hydrogen capable of reacting with the epoxy group in epoxy (73) Assignee: Chang Chun Plastics Co., Ltd. resin, and (21) Appl. No.: 09/794,835 (3) a hardener promoter. (22) Filed: Feb. 27, 2001 The flame-retardant resin composition described above has improved excellent heat resistance and flame retardant prop (30) Foreign Application Priority Data erty, and is especially Suitable for adhesive laminates, com posite materials, printed circuit boards, adhesive material for Jul. 19, 2000 (TW)...... 891.14433 copper foils, and is Suitable for IC packaging materials. US 2002/0032279 A1 Mar. 14, 2002

FLAME RETARDANT RESIN AND FLAME usually contains up to 17% to 21% of bromine and is used RETARDANT COMPOSITION CONTAINING THE in combination with antimonous acid anhydride or other SAME retardants to achieve the standard of UL 94V-0. However, the use of high contents of bromine in epoxy resin or BACKGROUND OF THE INVENTION antimonous acid anhydride will adversely affect the health of human body. AS well, bromine not only generates erosive 0001) 1. Field of the Invention free radicals and hydrogen bromide when it burns, aromatic 0002 The present invention relates to flame-retardant compounds with high bromine contents also produce toxic epoxy resins, and more particularly to a flame-retardant brominated furans and a brominated dioxine compound epoxy resin modified by a reactive phosphorus-containing during the burning process. Thus, Since both human health compound. and the environment are Seriously affected, it is necessary to find a novel flame retardant material and a flame retardant 0003 2. Background of the Invention property to Solve the pollution and environmental problems 0004 Conventional flame retardant compositions are caused by the current use of laminated products or compo generally added with flame retardant materials. Such as nents containing bromide or bromo-epoxy resin. Especially, halogen-containing compounds or antimony- or Vanadium it is necessary to actively develop flame retardant epoxy containing oxides to form high heat resistant compositions. resin materials which will not endanger humans and are The use of these materials, however, often causes Serious environmentally friendly to respond to the massive use of environmental pollution problems. electrical and electric products and components containing 0005. In the application of composite materials, as, for FR-4 epoxy glass fiber laminated plates. example in coating, electrical insulation, construction, build 0008 Thus, in order to protect human health and ing materials, adhesives or laminated products, epoxy resin decrease environmental pollution, a reactive type of flame composite materials are currently frequently used. Because retardant material has been developed. The technique using of easy processing, high Safety, excellent mechanical and phosphorus-containing compounds instead of bromine-con chemical properties, epoxy resins have been widely used in taining compounds (flame retardant materials convention many fields, and especially in the manufacture of laminated ally used) is widely accepted. The study and application of plates. Also, because epoxy resins have Strong adhesion to phosphorus System compounds for use as flame retardant reinforcement materials (such as glass-fiber fabrics), no materials that are environmentally friendly are currently Volatility matters, and Small shrinkage of the product while extensive, for example, red phosphorus or phosphorus hardening, laminated plateS produced by Such resins have containing organic compounds (such as triphenylphosphate, been massively applied to electrical and electronic products triphenylmethyl phosphate, etc.) are directly added to Sub or components. However, in order to prevent the products or Stitute halide as a flame retardant to improve the burning components from deterioration caused by the elevated tem property of polymer materials or hard resin materials. How perature during proceSS or use, additives Such as, for ever, it is necessary to add Such compounds in large amounts example, halogen compounds, phosphorus compounds or directly into resins to achieve flame retarding. The high oxides of antimony, Vanadium, etc., are generally added to migration due to the Smaller molecular weight of the com increase the heat resistance of the epoxy resins. pound will affect the properties of resin Substrates making, for example, electrical property, adhesive Strength, etc., 0006. In the current significant process of the printed inferior, resulting in difficulty of application. circuit board, the laminated plates are required to have excellent electrical properties, mechanical properties, and 0009. It is known that the technique employs a reactive heat resistant processing properties, in addition there is type of phosphorus-containing epoxy resin instead of the increased demand for finer patterns on the circuit board. For bromine-containing or bromo-epoxy resins generally used example, FR4 laminated plates, which are widely used, have as flame retardant ingredients, for example in U.S. Pat. No. a glass transition temperature of about 130 C. after hard 5,376,453, which utilizes the composition of phosphates ening. For the process of the printed circuit board, the having epoxy group and nitrogen-containing hardener to temperature is over 200 C. during cutting and drilling, and make laminated plates. It is necessary to add many kinds of even reaches over 270° C. during welding. Thus the lami phosphate-containing epoxy resin compositions to increase nated plates may break or crack during manufacture. In a phosphorus content that will achieve the high Standard of addition, for the laminated plates of printed circuit boards, UL94V-0. In U.S. Pat. No. 5,458,978, a composition formed another important property is flame retardancy. In Some from epoxy phosphates, nitrogen-containing epoxy resin, applications, Such as airplanes, automobiles, and public and metal complex hardener is used to make laminated transportation, the flame retardant property of the printed plates which has the flame retardant property approaching to circuit board is absolutely necessary. UL94V-0 (40 seconds, 50 seconds related to critical value). 0007. In order to impart a flame retardant property to In U.S. Pat. Nos. 4,973,631 and 5,086,156, a trialkyl oxide laminated plates, Substances that Separate the flame and having an active hydrogen Substituent (Such as amino group) decrease burning are introduced. For the laminated plates of is used alone or in combination with other amine hardeners epoxy resin/glass-fiber Systems (or organic fiber), halogen to harden epoxy resins. In these hardening methods of containing compounds, especially bromine-containing introducing phosphorus to resins, the low content of phos epoxy resins, and hardeners are used in combination with phorus is notable to achieve the flame retardant effect. There flame retardant material Such as antimonous acid anhydride, is no actual measurement of the flame retardant effect in etc., So that the achievement of flame retardant standards (as these two patents. strict as the UL94V-0 level) in the laminated plates can be 0010. In the techniques disclosed above it is usually attained. The flame retarding Substance in epoxy resin necessary to add many types of phosphorus-containing US 2002/0032279 A1 Mar. 14, 2002

compounds to meet the flame retardant Standard; however, 0015 The phosphorus-containing flame retardant resin additional additives usually make the processing conditions composition usually used in the process is a linear phos of products hard to control or the property of their products phorus-containing compound or non-reactive phosphorus inferior. containing compound resin compositions, which are much different in their processing properties. The phosphorus 0.011 Therefore, the method currently used to increase containing compound modified epoxy resin disclosed in the flame retardant property is to add nitrogen and phosphorus present invention has a flame retardant phosphorus-contain containing Substances instead of the currently used bromine ing Substance. Since the phosphorus-containing compound or antimony-containing Substances. The nitrogen-containing Side chain has a moiety which can react with the epoxy Substance frequently used is melamine, DICY, or cyanate group in epoxy resin, the difference in processing properties which contains a triazine ring. The phosphorus-containing will be small. As well, because side chain HCA molecular compound frequently used is a non-reactive phosphorus moiety may decrease the flowability, the molecules are more containing compound or a phosphorus-containing com Stable at high temperature and have higher heat resistance. pound which has a reactive functional group. Because the heat resistance of the non-reactive phosphorus-containing 0016. The epoxy resin having a phosphorus-containing compound is inferior to the reactive phosphorus-containing compound on the Side chain disclosed in the present inven compounds and is also more Stable for reactive phosphorus tion can replace the hardened resins containing bromide containing compounds binding to other molecules, the cur which are currently used in, for example, epoxy molding rent flame retardant materials used are mainly those using a compounds for IC packaging materials and composite mate reactive phosphorus-containing compound. The reactive rials. phosphorus-containing compound frequently used is linear. 0017. The phosphorus-containing compound epoxy resin The heat resistance of reactive phosphorus-containing com in the present invention can be added directly into thermo pound is inferior to that of the halogen-containing or non plastic resins, as in for example, polyol esters, polyethers, halogen-containing epoxy resin composition, due to the polyolefines, PEEK, PPE, POM, etc., or added directly to -O-P-O-bonds on the backbone chain. the compositions formed from Said resin, or react with Said 0012. The present invention discloses an epoxy resin resin to obtain phosphorus-containing compound resin com modified with a side chain having a reactive phosphorus positions. containing compound, wherein the reactive site which can 0018. The phosphorus-containing compound epoxy resin react with epoxy group in the epoxy resin in the Structure is and the composition thereof in the present invention have the phosphorus compound on the Side chain. The epoxy excellent heat resistance and flame retardant properties, can resin has better heat resistance than that of normal phos improve on the disadvantages of the known technology, and phorus-containing compound or epoxy resin, is Suitable for increase electrical and mechanical property as well as flame retardant composition, and can replace the materials decrease the cost of manufacture. The novel phosphorus containing halogen compounds without affecting the pro containing compound modified epoxy resin compositions cessing property while it achieves environmental protection. can be applied in the manufacture of prepregs, laminated plates, printed circuit boards, etc. which need to possess SUMMARY OF THE INVENTION flame retardant property, and they can be used in combina 0013 The present invention discloses an epoxy resin tion with other Said compositions to allow the laminated modified with a side chain having a reactive phosphorus plates to have a high glass transition temperature and containing compound and the composition thereof. It is excellent heat resistance. disclosed in the present invention that 9,10-dihydro-9-Oxa 10-phosphaphenanthrene-10-oxide (hereinafter, referred to DETAILED DESCRIPTION OF THE as HCA) having monofunctional reactivity is Subjected to an INVENTION addition reaction with reactive aldehyde to form a phospho 0019. The present invention relates to a flame retardant rus-containing compound having an alcohol group, and then resin, which is an epoxy resin with a side chain having Subjected to a condensation reaction with a compound reactive phosphorus-containing compounds and can replace having functional group Such as phenols, organic acids, and halide-containing resin or bromo-resin as a flame retardant the like; thus a reactive phosphorus-containing compound component without affecting the processing properties. on the Side chain is obtained. Such a phosphorus-containing compound can be used directly in the flame retardant resin 0020. Also, the present invention relates to a flame retar composition, and also can be applied to thermoplastic plas dant resin composition, which includes: tics or thermosetting resin compositions. 0021 (1) an epoxy resin with a side chain containing a reactive phosphorus-containing compound, 0.014 Generally, the epoxy resin with low bromine con tent used in copper clad laminate, build up, and Resin 0022 (2) a halogen-free hardener having a reactive Coated Copper (RCC) is obtained by reacting bisphenol type hydrogen capable of reacting with the epoxy group epoxy resin with tetrabromobisphenol. The bifunctional or in the epoxy resin, and polyfunctional phosphorus-containing compound disclosed in the present invention can be added directly to the resin 0023 (3) a hardening promoter. composition as a Substitute for tetrabromobisphenol or other 0024. The above flame retardant resin composition has bromine-containing compounds and phosphorus-containing the improved property of excellent heat resistance and flame compounds, or can be Subject to addition reaction with retarding. Said composition does not contain halogen, has epoxy resin to obtain phosphorus-containing compound excellent heat resistance and flame retardency and does not epoxy resin. need any additional flame retardant Substance. Also, the US 2002/0032279 A1 Mar. 14, 2002 halogen-free hardener described above may be phosphorus or nitrogen-containing compounds. -continued (R), 0.025 The epoxy resin modified with a side chain having a reactive phosphorus-containing compound and the com yr )-(3" position including Said resin are disclosed in the present \- - - invention, wherein the phosphorus-containing compound is (R) (R) (R) formed by Subjecting HCA to an addition reaction with reactive aldehyde to form an organic cyclic phosphorus compound, then Subjecting it to a condensation reaction with 0028 R is H, Co alkyl or aryl; R7 is -CH-, compounds having a functional group, Such as phenols, (CH4)2C-, -SO-, -CO-, -O-; R is -OH, organic acids, and the like; thus a Side chain having a -NH, -SH, -COOH, -SOH, -COH, or -NH reactive organic cyclic phosphorus compound thereon is COCH; m and n are integers from 0 to 4, Z is an integer obtained. For example, when HCA is subjected to an addi from 1 to 20, Epoxy- is a group containing at least one epoxy tion reaction with hydroxylbenaldehyde, then to a conden ring. sation reaction with phenols to give polyfunctional phos 0029) Clio alkyl represented by R in the above formula phorus-containing compounds, and when HCA is reacted is referred to as a linear or branched alkyl group having 1 to with glyoxal, then reacted react with phenols in a conden 10 carbon atoms, including methyl, ethyl, isopropyl, n-pro sation reaction, it yields polyfunctional phosphorus-contain pyl, n-butyl, Sec-butyl, tert-butyl, n-pentyl, isopentyl, ing compounds. The Structure of the polyfunctional phos n-hexyl, heptyl, octyl, nonyl, decyl, etc. phorus-containing compounds is similar to bisphenols, but HCA Substitutes one hydrogen atom or organic matter in the 0030) Aryl represented by R in the above formula is center of the Structure. The polyfunctional organic cyclic referred to as an aromatic group having 6 to 10 carbon phosphorus compounds can react with epoxy resins to atoms, including phenyl, naphthyl, etc. produce phosphorus-containing compound modified epoxy 0031. The phosphorus-containing compound modified resins (hereinafter Sometimes referred to as flame retardant epoxy resin is prepared by reacting a phosphorus-containing phosphorus-containing epoxy resins). compound of formula (B), 0026. The phosphorus-containing compound modified epoxy resin disclosed in the present invention is represented by the formula (A) (B)

(A) OP-O RS-Arl-CH-Ar2-R5

ORP 0032) wherein R is a group selected from -OH, -NH2, Epoxy-R-Ari dHAr-R5-Epoxy -SH, -COOH, -SOH, -COH, and -NHCOCH while Ar' and Art are independently selected from the following groups: 0027) wherein Ris a group selected from -O-, NH-, -S-, COO-, -SO-, -CO-, and -CHCON<; Ar' and Arfare independently selected from the groups as follow: 5 y (R)S-S-ea (R) -(R) NQM y1

(R)nCC (R), (R)

1s | 1s Y& N Rt7

(R)n (R), (R), . (R) US 2002/0032279 A1 Mar. 14, 2002

0042. The embodiments of phenyl polyhydroxyphenol -continued polyglycidyl ether include tris(4-hydroxyphenyl)methane (R), polyglycidyl ether, tris(4-hydroxyphenyl)ethane polygly cidyl ether, tris(4-hydroxyphenyl)propane polyglycidyl ether, tris(4-hydroxyphenyl)butane polyglycidyl ether, tris(3-methyl-4-hydroxyphenyl)methane polyglycidyl ether, i. tris(3,5-dimethyl-4-hydroxyphenyl)methane polyglycidyl ether, tetrakis(4-hydroxyphenyl)ethane polyglycidyl ether, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane polyglycidyl 0033 R is H, Co alkyl or aryl; R is -CH-, ether, bicyclopentene-phenolic polyglycidyl ether, etc. (CH4)2C-, -SO-, -CO-, -O-; R is -OH, 0043. The embodiments of glycidyl ethers containing a NH, -SH, -COOH, -SOH, -COH, or -NH COCH; m and n are integers from 0 to 4, Z is an integer nitrogen hetero ring include triglycidyl ether of isocyanu from 1 to 20, with either an epoxy resin containing at least rate, triglycidyl ether of cyanurate, etc. two epoxy groups or with an epihalohydrin. 0044) The embodiments of dihydroxynaphthalene gly cidyl ethers include 1,6-dihydroxynaphthalene diglycidyl 0034) The phosphorus-containing compound (B) ethers, 2,6-dihydroxynaphthalene diglycidyl ethers, etc. described above is obtained by addition reacting HCA as represented by formula (C), 004.5 The epoxy resins described above can be used alone or in combination as the mixture of two or more. Among them, bisphenol A glycidyl ether, phenolic polyg lycidyl ether, tris(4-hydroxyphenyl)methane polyglycidyl (C) ether, bicyclopentene-phenolic polyglycidyl ether, tetralis(4- hydroxyphenyl)ethane polyglycidyl ether, and the mixtures thereof are preferred. 0046) The manufacture of the flame retardant resin of the present invention optionally includes other compounds con taining active hydrogens, for example, amines, bisphenol resins, dihydroxybenzene, polyhydroxyphenol resins, phe nolics, etc. 0.035 with a compound containing a C=O reactive 0047 The embodiments of amines include dicyanodia group (for example, aldehydes, etc.) to form a phosphorus mide, diaminodiphenylmethane, etc. containing compound having an alcohol group, then con 0048. The embodiments of bisphenol resins include com densation reacting it with a compound Such as phenols, pounds represented by -Ph-X-Ph- (wherein Ph repre organic acids, or the like to give the phosphorus-containing Sents phenylene, X is -CH2-, -C(CH-)-, -O-, compound represented as formula (B). -S-, -CO-, or -SO-), for example, bisphenol A, 0.036 The embodiments of the epoxy resin containing at bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphe least two epoxy groups include bisphenol glycidyl ether, nol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, biphenylglycidyl ethers, dihydroxybenzene glycidyl ethers, tetramethyl bisphenol S, 4,4'-biphenyl, 3,3'-dimethyl-4,4'- glycidyl ethers containing nitrogen hetero ring, dihydrox biphenyl, 3,3',5,5'-tetramethyl-4,4'-biphenyl, etc. ynaphthalene glycidyl ethers, phenolics polyglycidyl ethers, 0049. The embodiments of dihydroxybenzene include polyhydroxyglycidyl ethers, etc. resorcinol, quinol, isobutyldihydroxybenzene. 0037. The embodiments of the epihalohydrin include 0050. The embodiments of poly(hydroxyphenol) resin epichlorohydrin and epibromohydrin. include tris(4-hydroxyphenyl)methane, tris(4-hydroxyphe 0.038. The embodiments of bisphenol glycidyl ethers nyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydrox include bisphenol A glycidyl ethers, bisphenol F glycidyl yphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, ethers, bisphenol AD glycidyl ethers, bisphenol Siglycidyl tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hy ethers, tetramethyl bisphenol A glycidyl ethers, tetramethyl droxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphe bisphenol F glycidyl ethers, tetramethyl bisphenol AD gly nyl)ethane, etc. cidyl ethers, tetramethyl bisphenol Siglycidyl ethers, etc. 0051. The embodiments of phenolics include phenol formaldehyde condensate, creSol phenolic condensate, 0039. The embodiments of biphenyl glycidyl ethers bisphenol A phenolic condensate, bicyclopentene-phenolic include 4,4'-biphenyl glycidyl ether, 3,3'-dimethyl-4,4'-bi phenyl glycidyl ether, 3,3',5,5'-tetramethyl-4,4'-biphenyl condensate. glycidyl ether, etc. 0052 Among these, bisphenol A, bisphenol F., bisphenol AD, bisphenol S, tetramethyl bisphenol A, and resorcinol 0040. The embodiments of dihydroxybenzene glycidyl biphenol are preferred. ethers include resorcinol glycidyl ether, quinol glycidyl ether, isobutyldihydroxybenzene glycidyl ether, etc. 0053. In the production of the flame retardant epoxy resins of the present invention, the equivalent weight ratio of 0041. The embodiments of phenolic polyglycidyl ethers the above-mentioned components, epoxy resin (or epihalo include phenolic polyglycidyl ether, creSol phenolic polyg hydrin): HCA, is 100:5 to 100:150, preferably 100:10 to lycidyl ether, bisphenol A phenolic polyglycidyl ether, etc. 100:50, more preferably 100:15 to 100:40. When the relative US 2002/0032279 A1 Mar. 14, 2002 ratio of the phosphorus-containing compound is more than bisphenol F glycidyl ethers, tetramethyl bisphenol AD gly 150, the solubility of the resin solvent decreases and the cidyl ethers, tetramethyl bisphenol S glycidyl ethers, etc. viscosity of the resin Solution increases. When the relative ratio of phosphorus-containing compounds is less than 5, the 0064. The embodiments of biphenyl glycidyl ethers flame retardant property of the product is inferior. include (4,4'-biphenyl)glycidyl ether, 3,3'-dimethyl-(4,4'- biphenyl) glycidyl ether, 3,3',5,5'-tetramethyl-(4,4'-biphe 0.054 The reaction for producing the flame retardant phosphorus-containing epoxy resin can be advancement nyl)glycidyl ether, etc. reaction or reflux reaction, wherein the reflux reaction is the 0065. The embodiments of dihydroxybenzene glycidyl process of reaction in which the solvent refluxes. The ethers include 1,3-dihydroxybenzene glycidyl ether, 1,4- Suitable Solvents are ketones, organic aromatics, non-proton dihydroxybenzene glycidyl ether, 5-isobutyl-1,3-dihydroxy Solvents, ethers, and esters. Among organic aromatics, tolu benzene glycidyl ether, etc. ene and Xylene are preferred. Among ketones, acetone, methyl ethyl ketone, and methyl isobutyl ketone are pre 0066. The embodiments of phenolic polyglycidyl ethers ferred. Among non-proton solvents, N,N-dimethylforma include phenolic polyglycidyl ether, creSol phenolic polyg mide, N,N-diethylformamide, and dimethyl sulfoxide are lycidyl ether, bisphenol A phenolic polyglycidyl ether, etc. preferred. Among ethers, ethylene glycol monomethyl ether and propylene glycol monomethyl ether are preferred. 0067. The embodiments of phenyl polyhydroxyphenol Among esters, ethyl acetate, ethyl isopropionate, and pro polyglycidyl ether include tris(4-hydroxyphenyl)methane pylene glycol monomethyl ether acetate are preferred. polyglycidyl ether, tris(4-hydroxyphenyl)ethane polygly 0055 The reaction of compound.(B) and the epoxy resin cidyl ether, tris(4-hydroxyphenyl)propane polyglycidyl having at least two epoxy group is generally conducted at a ether, tris(4-hydroxyphenyl)butane polyglycidyl ether, temperature of 50 to 350° C., preferably 50 to 300° C., more tris(3-methyl-4-hydroxyphenyl)methane polyglycidyl ether, preferably 100 to 250° C., most preferably 100 to 200° C. tris(3,5-dimethyl-4-hydroxyphenyl)methane polyglycidyl under an normal pressure. When the reaction temperature is ether, tetrakis(4-hydroxyphenyl)ethane polyglycidyl ether, higher than 350° C., the by-products are easily formed and tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane polyglycidyl it is difficult to control the reaction Speed; as well, deterio ether, bicyclopentene-phenolic polyglycidyl ether, etc. ration of the resins may possibly be accelerated. When the 0068 The embodiments of glycidyl ethers containing reaction temperature is lower than 50 C., the reaction aZa-heterocyclic ring include triglycidyl ether of isocyanu efficiency will be poor and it will be difficult for the resulting resins to meet the requirement for application at high rate, triglycidyl ether of cyanurate, etc. temperature. 0069. The embodiments of dihydroxynaphthalene gly 0056 The reaction of compound (B) and the epihalohy cidyl ethers include 1,6-dihydroxynaphthalene diglycidyl drin is generally conducted at a temperature of 50 to 350° C., ethers, 2,6-dihydroxynaphthalene diglycidyl ethers. preferably 50 to 300° C., more preferably 100 to 250° C., 0070 The epoxy resins can be used alone or in combi most preferably 100 to 200 C. under a reduced pressure. nation as the mixture of two or more epoxy resins. 0057 The present invention also relates to a flame 0071. The preferred embodiments are bisphenol A gly retardant resin composition comprising: cidyl ether, phenolic polyglycidyl ether, creSol phenolic 0.058 (1) the above-mentioned epoxy resin modified polyglycidyl ether, tris(4-hydroxyphenyl)methane polygly by a Side chain containing a reactive phosphorus cidyl ether, bicyclopentene-phenolic polyglycidyl ether, tet containing compound of the present invention, rakis(4-hydroxyphenyl)ethane polyglycidyl ether, and the mixtures thereof. 0059 (2) a halogen-free hardener having an active hydrogen capable of reacting with the epoxy group 0072 According to the present invention, the content in the epoxy resin, and ratio of the flame retardant phosphorus-containing epoxy resin to the non-phosphorus-containing epoxy resin men 0060 (3) a hardening promoter tioned above is Such that the flame retardant phosphorus 0061. In addition to the epoxy resin with a side chain containing epoxy resin is from 5 to 100 wt %, preferably having a reactive phosphorus-containing compound of the from 20 to 100 wt %, and more preferably from 25 to 100 present invention, the flame retardant resin composition also wt % of the total epoxy resin composition. If the ratio of may contain other epoxy resins containing no phosphorus. content is less than 5 wt %, the flame retardant property and heat resistance will not be sufficient. 0062) The epoxy resins containing no phosphorus may be any epoxy resin. The embodiments include bisphenol gly 0073. The hardeners in the flame retardant and heat cidyl ether, biphenyl glycidyl ethers, dihydroxybenzene resistant epoxy resin compositions of the present invention glycidyl ethers, glycidyl ethers containing the nitrogen het comprise the phosphorus- or nitrogen-containing hardeners ero ring, dihydroxynaphthalene glycidyl ethers, phenolics which contain a compound with an active hydrogen which polyglycidyl ethers, polyhydroxyphenol polyglycidyl can react with an epoxy group and other halogen-free ethers, etc. hardenerS. 0.063. The embodiments of bisphenol glycidyl ethers 0074 The useful nitrogen- and phosphorus-containing include bisphenol A glycidyl ethers, bisphenol F glycidyl resin hardeners in the flame retardant resin composition of ethers, bisphenol AD glycidyl ethers, bisphenol Siglycidyl the present invention have the Structure represented by ethers, tetramethyl bisphenol A glycidyl ethers, tetramethyl formula (D), US 2002/0032279 A1 Mar. 14, 2002

0082 The embodiments of amines comprise dicyanodia mide, diaminodiphenylmethane, etc. (D) 0083. The embodiments of bisphenol resins comprise compounds represented by -Ph-X-Ph- (wherein Ph represents phenylene, X is -CH2-, -C(CH-)--, -O-, -S-, -CO-, or -SO-), for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphe nol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, (4,4'-biphenyl), 3,3'-dimethyl-4,4'- biphenyl, 3,3',5,5-tetramethyl-(4,4'-biphenyl), etc. 0075) wherein R is selected from hydrogen atom or any structure of formulas (E) or (E), but where at least one R' 0084. The embodiments of dihydroxybenzene include is not a hydrogen atom.: resorcinol, quinol, isobutylquinol. 0076 (E) R'=-CH-R, H, wherein R is phe 0085 The embodiments of poly(hydroxyphenol) resin nylene, naphthylene, or the group of the following formula, include tris(4-hydroxyphenyl)methane, tris(4-hydroxyphe nyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydrox yphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hy droxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphe nyl)ethane, etc. ŽScy. 0086 The embodiments of phenolics include phenol formaldehyde condensate, creSol phenolic condensate, bisphenol A phenolic condensate, bicyclopentene-phenolic 0.077 wherein A is -O-, -S-, -SO-, -CO-, condensate. -CH-, -C(CH)-, or the group of the formula: 0087. The hardener content in the flame retardant resin compositions of the present invention depends on the equivalent weight of the reactive hydrogen in the hardeners and the epoxy equivalent weight in the epoxy resins. In the -ci- Y-ch- a -?. -H epoxy equivalent weight in the epoxy resins, the equivalent weight of the reactive hydrogen in the hardenerS is 20 to -(-)--- (Old 140%, preferably 40 to 95%, more preferably 50 to 95%. (R'), 0088. The embodiments of the hardening promoters con tained in the flame retardant resin composition comprise 0078) R' is H, Co is an alkyl or aryl; Y is -OH, tertiary amines, tertiary phosphines, quaternary ammonium -NH, -COOH, a is an integer of 0 to 2; x is an integer Salts, quaternary phosphonium Salts, boron trifluoride com of 0 to 4; among the groups represented by R and A plex, lithium compounds, imidazole compounds, and the described above, the aryl may be substituted by one or more mixture thereof. Substituents Selected from a hydroxy, amino, carboxy, or a Caliphatic group. 0089. The embodiments of the tertiary amines comprise triethylamine, tributylamine, dimethylethanolamine, dim 0079 (E) ethylphenylamine, tris(N,-dimethylaminomethyl)phenol, N,N-dimethylaminomethylphenol, etc. 0090 The embodiments of the tertiary phosphines com O prise triphenylphosphine. | - -CH-R-CH2-- 0091. The embodiments of the quaternary ammonium Salts comprise tetramethylammonium chloride, tetramethy lammonium bromide, tetramethylammonium iodide, trieth ylbenzylammonium chloride, triethylbenzylammonium bro mide, triethylbenzylammonium iodide, etc. 0092. The embodiments of the quaternary phosphonium Salts comprise tetrabutylphosphonium chloride, tetrabu 0080 R is -NHR', C alkyl or aryl; n is an integer of tylphosphonium bromide, tetrabutylphosphonium iodide, 0-20; but at least one R' is not a hydrogen atom. The tetrabutylphosphonium acetate complex, tetraphenylphos definitions of R and n in formula (E) are respectively the phonium chloride, tetraphenylphosphonium bromide, tet same as those in the above formula (E). raphenylphosphonium iodide, ethyltriphenylphosphonium 0081. The other halogen-free hardeners which can react chloride, ethyltriphenylphosphonium bromide, ethyltriph with epoxy groups in the flame retardant resin composition enylphosphonium iodide, ethyltriphenylphosphonium of the present invention include amines, bisphenol resins, acetate complex, ethyltriphenylphosphonium phosphate dihydroxybenzene, polyhydroxyphenol resins, and pheno complex, propyltriphenylphosphonium chloride, propylt lics. riphenylphosphonium bromide, propyltriphenylphospho US 2002/0032279 A1 Mar. 14, 2002 nium iodide, butyltriphenylphosphonium chloride, butylt 0100. The phosphorus-containing compound modified riphenylphosphonium bromide, butyltriphenylphosphonium epoxy resin compositions having heat resistance and flame iodide, etc. retarding property of the present invention are useful for manufacturing laminated plates or adhesive plates, which 0093. The imidazole compounds comprise, for example, may use impregnated organic or inorganic fiber Substrates, 2-methylimidazole (2MI), 2-phenylimidazole (2PI), 2-ethyl for example, glass, metal, carbon fiber, aramid, borides, 4-methylimidazole (2E4MZ), CMI, C.MI, etc. Said hard cellulose. ening promoters can be used alone or in combination with two or more mixtures. 0101 The flame retardant resin compositions of the 0094. The preferred hardening promoters are tertiary present invention can be manufactured by conventional amines, tertiary phosphines, and imidazole compounds, methods into laminated entities of copper foil, fiber Sup especially dimethylaniline, 2-methylimidazole (2MI), ports, and the flame retardant resin compositions of the 2-phenylimidazole (2PI), 2-ethyl-4-methylimidazole present invention. (2E4MZ). 0102) The phosphorus-containing epoxy resin flame retardant compositions of the present invention can be 0.095 The amount of the hardening promoters used is formulated with the nitrogen-containing epoxy resin into from 50 to 50000 ppm, preferably from 100 to 30000 ppm, varnish, with which glass fiber fabric or organic fiber is more preferably from 200 to 10000 ppm, and most prefer impregnated, then dried by heating, giving a dry prepreg. ably from 500 to 2000 ppm of the total weight of the The prepreg can further be shaped into composite material composition. If the added amount of the hardening promot laminated plates or used alone in the adhesive layer of other ers is more than 50000 ppm, the reaction time will decrease laminated plates. Alternatively copper foil maybe placed on but the application properties will be affected due to the one side or both sides of a prepreg or the combination of formation of by-products. For example, in the application more prepregs, and the prepreg or the combination may be for circuit board laminated plates, the electrical property, heated under pressure. The laminated plate composite mate resistance to wetting, water absorption, etc. will deteriorate. rial thus obtained is Superior to the Standards of the current If the added amount is less than 50 ppm, the reaction time products in respect to Size Stability, resistance to chemicals, will be slow and inefficient. resistance to corrosion, moisture absorption, and electrical 0096. The flame retardant resin compositions of the properties, and is Suitable for producing electrical products present invention have excellent heat resistance and flame for electronic, Space, and transport, and for manufacturing retardant properties, and, after hardened by hardeners, are printed circuit boards and multi-layer circuit boards. The Suitable for high heat resistant materials, for example, adhe useful impregnated fiber Substrates are organic or inorganic Sive plates or prepregs, composite materials, laminated fiber Substrates, comprising, for example, glass fiber, metal plates, printed circuit boards, copper foil adhesives for resin fiber, carbon fiber, aramid fiber, boron, cellulose, etc. coated copper foil (RCC), epoxy resin modeling compounds 0.103 Alternatively, the flame retardant and heat resistant in IC package materials (EMC's), high heat resistant powder resin compositions of the present invention can be formu coatings, engineering plastics, etc. The components in the lated into varnish, where the varnish is coated on copper foil, composition will depend on the usage. then dried by heating, yielding dry film-coated copper foil. 0097. Additionally, in the epoxy resin composition modi The film-coated copper foil can be Stored at room tempera fied with the phosphorus-containing compound of the ture for months and has good Stability in Storage. The present invention, the Viscosity can be adjusted by the film-coated copper foil can be further shaped into composite addition of a Solvent to formulate the composition into material laminated plates or used alone in the adhesive layer Varnish. The Suitable Solvents include organic benzenes, of other plastic plates, or it can be used in combination with ketones, non-proton Solvents, ethers, and esters. Organic one or more film-coated copper foils which are built-up benzenes include, for example, toluene and Xylene. Ketones one-by-one on the up side or on both the up and down sides. acetone, methyl ethyl ketone, and methyl isobutyl ketone. The laminated plate composite material thus obtained is Aprotic solvents include, for example, N,N-dimethylforma Superior to the Standards of the current products in respect to mide, N,N-diethylformamide, and dimethyl sulfoxide. Size Stability, resistance to chemicals, resistance to corro Ethers include, for example, ethylene glycol monomethyl Sion, moisture absorption, and electrical properties, and is ether and propylene glycol monomethyl ether. Esters Suitable for producing multi-layer printed circuit boards for include, for example, ethyl acetate, ethyl isopropionate, and electronics, Space, and transport. propylene glycol monomethyl ether acetate. The Viscosity is 0104. Also, the present invention relates to a method mainly controlled in the range of 20 to 500 cps/25 C. during which uses the flame retardant resin composition to produce the formation. hardened entities, wherein the composition is hardened at a 0.098 Generally, the addition of the hardening promoters reaction temperature of from 20 to 350° C., preferably from and the selective addition of solvents are preferred to allow 50 to 300° C., more preferably from 100 to 250° C., most the gelling time of Said flame retardant resin varnish to be preferably from 120 to 220 C. Thabove-mentioned reaction controlled in the range of 30 to 500 sec/171. C. where the temperature for hardening must be controlled carefully. If viscosity is controlled in the range of 20 to 500 cps/25 C. the temperature is too high, there will easily be a side reaction where it will be difficult to control the reaction 0099. According to the application, general additives and Speed, thus increasing the deterioration Speed of the resin. If modifiers, Such as, for example, heat Stabilizers, light Sta the temperature is too low, in addition to the poor efficiency, bilizers, UV absorbents, plasticizers, etc., can also be added it will be difficult for the properties of the resulting resin to to the compositions of the present invention. meet the requirements for usage under high temperature. US 2002/0032279 A1 Mar. 14, 2002

0105. According to the flame retardant and heat resistant C. for 4 hours, while its viscosity is measured at 25 resin composition of the present invention, the flame retar C. with a Brookfield viscosimeter. dant property and the heat resistance of epoxy resins will be maintained without adding other processing auxiliary agents 0121 (3) Solid content: 1 gram of the varnish and flame retardant additives. Sample containing the phosphorus-containing epoxy 0106 The present invention will be further described resin of the present invention is placed in an oven at with reference to the following Examples, but the Scope of 150° C. for 60 minutes after which and the weight the present invention is by no means limited. percentage of the resulting non-volatile components 0107 The components used in the Synthesis Examples is measured. and the Examples are described in detail as follow: SYNTHESIS EXAMPLE 1. 0108 Epoxy resin 1: an epoxy resin produced by Chang Chun Plastics Co., Ltd. Taiwan under trade name Synthesis of Phosphorus-containing Compound CNE200ELB, which is a polyglycidyl ether of a cresol phenolic condensate. The epoxy equivalent weight is HCP between 200 and 220 g/eq, and the hydrolytic chlorine is 0.122 216 g of organic cyclic phosphorus compound under 200 ppm. HCA (9,10-dihydro-9-Oxa-10-phosphaphenanthrene-10-ox 0109 Epoxy resin 2: an epoxy resin produced by Chang ide) was placed in a glass reaction kettle and stirred to melt. Chun Plastics Co., Ltd. Taiwan under trade name PNE177, When the temperature reached 110° C., 32.6 g of polyform which is a phenolic polyglycidyl ether. The epoxy equivalent aldehyde (produced by Chang Chun Plastics Co., Ltd. Tai weight is between 170 and 190 g/eq, and the hydrolytic wan, Paraformaldehyde 92%) was added, the temperature chlorine is under 1000 ppm. was elevated to 150 C., and the reaction was continued for 0110 Epoxy resin 3: an epoxy resin produced by Chang more than 3 hours. After the pressure was decreased to 20 Chun Plastics Co., Ltd. Taiwan under trade name BE188EL, mmHg and kept for 1 hour, yielding 246 g of organic cyclic which is a bisphenol A diglycidyl ether. The epoxy equiva phosphorus compound HCAL, 246 g of toluene was added. lent weight is between 180 and 195 g/eq, and the hydrolytic The toluene was heated and Stirred to dissolve in the glass chlorine is under 200 ppm. reaction kettle. When the temperature reached 110° C., 94 g 0111 Epoxy resin 4: an epoxy resin produced by Chang of phenol and 2.5 g of p-toluenesulfonic acid were added, Chun Plastics Co., Ltd. Taiwan under trade name and the reaction was continued for 3 hours. Then the reaction BEB530A80, which is a diglycidyl ether of tetrabromo was cooled down to the room temperature, the reaction bisphenol A. The epoxy equivalent weight is between 430 mixture was filtered and dried to give an organic cyclic and 450 g/eq, while the bromine content is between 18.5 and phosphorus compound referred to as HCP. 20.5 wt %. 9,10-dihydro-9-Oxa-10-phosphaphenan 0123 The organic cyclic phosphorus compound HCP 0112] HCA: formed in the above-mentioned reaction has a melting point threne-10-oxide. of 146 C. The result of the elementary analysis is as follow: 0113 Catalyst A (also referred to as a hardening pro moter): triphenyl phosphine, 10% dissolved in methyl ethyl ketone. 0114 Catalyst B: 2-methylimidazole (2MI), 10% dis C% H% P% Found: 74.3% 4.9% 10.2% solved in methyl ethyl ketone. Calculated: 74.51% 4.9% 10.13% 0115 Hardener A. dicyanodiamide, 10% dissolved in (CoHsOP formula weight = 306) dimethyl formamide. 0116 Hardener B: produced by Hitachi Chemical Co., Japan under trade name melan 9000TM79. SYNTHESIS EXAMPLE 2 0117 Hardener C: produced by Chang Chun Plastics Co., Ltd. Taiwan under trade name BEH510. The active hydro Synthesis of Phosphorus-containing Compound gen equivalent weight is between 105 and 110 g/eq. HDP 0118 Epoxy equivalent weight (EEW), viscosity of var 0124 Organic cyclic phosphorus compound HCA (216 nish, Solid content used herein are measured according to the g) placed in a glass reaction kettle was heated and stirred to methods as follow: melt. When the temperature reached 110° C., 72.5g of 40% 0119 (1) Epoxy equivalent weight: the epoxy resin glyoxal was added, and the reaction was continued for more is dissolved in the solvent of chlorobenzene:chloro than 3 hours. Then the reaction was cooled down to the room form (1:1) and titrated with HBr/glacial acetic acid temperature, the reaction mixture was filtered and dried to according to the method in ASTM D1652 to measure give an organic cyclic phosphorus compound referred to as epoxy equivalent weight, wherein the indicator is HCAG. crystal violet. 0.125 The organic cyclic phosphorus compound HCAG 0120 (2) Viscosity: the phosphorus-containing formed in the above-mentioned reaction has a melting point epoxy resin varnish is placed in a thermostat at 25 of 243 C. The result of the elementary analysis is as follow: US 2002/0032279 A1 Mar. 14, 2002

SYNTHESIS EXAMPLE 4 Synthesis of Phosphorus-containing Epoxy Resin A C% H% P% Found: 63.9% 4.1% 12.5% 0131 Epoxy resins (100 g) and organic cyclic phospho Calculated: 63.67% 4.08% 12.65% rus compound HPP (380.5 g) were placed in a 3000 ml of (C2H2O.P. formula weight = 490) five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric Stirrer 0.126 245 g of organic cyclic phosphorus compound and a stirring bar, a nitrogen gas inlet, a thermocouple, a HCAG and 245 g of toluene were placed in the glass water-cooled condenser, and a feeding funnel. Nitrogen gas reaction kettle, heated, and stirred to dissolve. When the was introduced and the reaction kettle was heated to 120° C. temperature reached 110° C., 94 g of phenol and 2.5 g of After epoxy resin 3 and HCA completely melted, the raw p-tolueneSulfonic acid were added, and the reaction was materials were dried under vacuum. The Steps of introducing continued for more than 3 hours. After the reaction was nitrogen gas and drying were carried out two more times. cooled down to room temperature, the reaction mixture was When the temperature of the reaction kettle was decreased filtered and dried to give an organic cyclic phosphorus from 85 to 90° C., catalyst A (6.0 g) was added. The stirrer compound referred to as HDP. was started to mix the resin and catalyst and the nitrogen gas 0127. The organic cyclic phosphorus compound HDP was introduced. The resulting mixture was heated to 160° C. formed in the above-mentioned reaction has a melting point and kept for 10 minutes. It was found that the reactants were of 260C. The result of the elementary analysis is as follow: Slowly exothermic. After the exothermic reaction continued and the temperature rose to 180° C., this temperature was kept for 3 hours and phosphorus-containing epoxy resin A C% H% P% was obtained. The epoxy equivalent weight was 396, and the theoretical phosphorus content was 2.0 wt %. Found: 71.2% 4.4% 9.6% Calculated: 71.03% 4.36% 9.66% (CH2O.P. formula weight = 642) SYNTHESIS EXAMPLES 5 TO 7 0132) The reaction of this synthesis example was similar to Synthesis example 1, but after the reaction, the Solvents SYNTHESIS EXAMPLE 3 shown in table 1 were added to the resulting epoxy resin, yielding phosphorus-containing resin in Solution form. The Synthesis of Organic Cyclic Phosphorus-containing epoxy equivalent weights, Solid contents, and theoretical Compound HPP phosphorus contents of the resulting phosphorus-containing 0128 Organic cyclic phosphorus compound HCA (216 resin in Synthesis Examples 2 to 4 are shown in table 2. g) placed in a glass reaction kettle was heated and stirred to melt. When the temperature reached 110° C., 112 g of TABLE 1. 4-hydroxybenzaldehyde was added, and the reaction then continued for more than 3 hours. After the reaction was Formulations of Synthesis Examples 4 to 7 cooled down to the room temperature, the reaction mixture Synthesis Synthesis Synthesis Synthesis was filtered and dried to give an organic cyclic phosphorus Example Example Example Example compound referred to as HCAB. M.p.=212 C. Phosphorus- Phosphorus- Phosphorus- Phosphorus Containing Containing Containing Containing 0129. The organic cyclic phosphorus compound HCAB Epoxy Epoxy Epoxy Epoxy (338 g) and toluene (338 g) were placed into a glass reaction Resin A Resin B Resin C Resin D kettle and heated under Stirring. When the temperature reached 110° C., 94 g of phenol and 3.4 g of p-toluene Epoxy Resin 362 Sulfonic acid were added, and the reaction was continued for 1 (g) further more than 3 hours. The reaction mixture was cooled Epoxy Resin 360 down to room temperature, filtered and dried to give an 2 (g) Epoxy Resin 1OOO 640 1OOO 625 organic compound referred to as HPP. 3 (g) 0130. The organic cyclic phosphorus compound HPP HPP (g) 380.5 380.5 454 380.5 Bisphenol 13 formed in the above-mentioned reaction has a melting point A (g) of 286 C. The result of the elementary analysis is as follow: Catalyst 6.O 6.O 6.O 5.9 A (g) Propylene 230 230 242.3 230 glycol C% H% P% Monomethyl Found: 72.7% 4.6% 7.4% ether Calculated: 72.46% 4.59% 7.49% acetate (ml) (Cas HoOP formula weight = 414) Acetone (ml) 230 230 242.3 230 US 2002/0032279 A1 Mar. 14, 2002 10

0133) under stirring. When the temperature reached 110° C., 112 g of 4-hydroxybenzaldehyde was added and the reaction was TABLE 2 continued further for more than 3 hours. Then the reaction Property Test of Phosphorus-Containing Epoxy Resins was cooled down to the temperature, the reaction mixture was filtered and dried to obtain an organic cyclic phosphorus Phosphorus- Phosphorus- Phosphorus- Phosphorus Containing Containing Containing Containing compound referred to as HCAB. M.p.=212 C. Epoxy Epoxy Epoxy Epoxy Resin A Resin B Resin C Resin D 0.137 The organic cyclic phosphorus compound HCAB (338 g) and toluene (338 g) were placed into a glass reactor Epoxy 396 389 472 4.38 Equivalent kettle and heated under Stirring. When the temperature Weight (g?eg) reached 110° C., 108 g of o-cresol and 3.4 g of p-toluene Solid Content 74.9% 74.7% 75.1% 75.0% Sulfonic acid were added, and the reaction was continued further for more than 3 hours. After the reaction mixture was cooled down to room temperature, filtered and dried to give SYNTHESIS EXAMPLE 8 an organic cyclic phosphorus compound referred to as BPC. Synthesis of Phosphorus- and Nitrogen-containing M.p.-245° C. Hardener D 0.138. The organic cyclic phosphorus-containing com 0134) 1410 g of phenol (15 moles), 244.7 g of 92% pound HPC (428 g) and epichlorohydrin (92.5 g) were placed paraformaldehyde (7.5 moles), 337 g of benzoguanamine into a glass reactor kettle, Stirred and heated to a temperature (1.8 moles), 259 g of HCA (1.2 moles), and 11.2 g of oxalic acid in a 3000 ml of five-neck glass reaction kettle equipped of 55 C. 49.5 wt % aqueous solution of sodium hydroxide with an electric heating jacket, a temperature controller, an (153.5 g) was added to the mixture and reacted at that electric Stirrer and a stirring rod, a nitrogen gas inlet, a temperature for 5 hours under a reduced pressure. The thermocouple, a water-cooled condenser, and a feeding resultant reaction mixture was heated under a vacuum to funnel. After melting, the raw materials were dried under recover unreacted epichlorohydrin. After the temperature Vacuum. The Steps of introducing nitrogen gas and drying reached 155 C., the pressure was released. Water and the row materials under a vacuum were carried out two more methyl isobutyl ketone were added to the reaction mixture to times after the temperature of the reaction kettle was effect the extraction. Aqueous phase was separated and the elevated from 100 to 110° C., and kept for 3 hours, then the organic phase was evaporated to give 518 g of a phosphorus temperature of the reaction kettle was elevated from 120 to containing epoxy resin of the present invention (referred to 125 C., and kept for 2 more hours. After the reaction, the as CEP-280). The phosphorus-containing epoxy resin has an unreacted phenol and reacted condensed water were slowly epoxy equivalent of 300 g/eq and a softening point of 95 C. distilled off under normal pressure. Finally, the mixture was kept at 180° C. under a vacuum for 1 hour. The resulting EXAMPLE 1 TO 7 AND COMPARATIVE product was phosphorus- and nitrogen-containing hardener EXAMPLE D. After analysis, the softening point was 161° C. While theoretical nitrogen content was 10.0 wt %, and the phos 0.139. In a kettle equipped with a mixer and a condenser, phorus content was 2.93 weight %, the active hydrogen the above-synthesized phosphorus-containing epoxy resins, equivalent weight is 210 g/eq. hardeners, hardening promoters, and Solvents were formu SYNTHESIS EXAMPLE 9 lated at room temperature according to the ratios shown in Table 1 into epoxy resin varnish. Synthesis of Phosphorus-Containing Epoxy Resin 0.135 The organic cyclic phosphorus-containing com TABLE 3 pound HPP (414 g, produced in Synthesis Example 3) and epichlorohydrin (925 g) were placed into a glass reactor Comp. kettle, stirred and heated to a temperature of 55 C. 49.5 wt Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex % aqueous solution of sodium hydroxide (153.5 g) was Varnish Formulation added to the mixture and reacted at that temperature for 5 hosphorus- 125 hours under a reduced preSSure. The resultant reaction ontaining mixture was heated under a vacuum to recover unreacted : poxy Resin epichlorohydrin. After the temperature reached 155 C., the A. (g) hosphorus 125 preSSure was released. Water and methyl isobutyl ketone ontaining were added to the reaction mixture to effect the extraction. poxy Resin Aqueous phase was separated and the organic phase was (g) evaporated to give 518 g of a phosphorus-containing epoxy hosphorus 125 125 125 ontaining resin of the present invention (referred to as BEP-270). The poxy Resin phosphorus-containing epoxy resin has an epoxy equivalent (g) of 288 g/eq and a softening point of 85 C. hosphorus 125 125 ontaining SYNTHESIS EXAMPLE 10 poxy Resin Synthesis of Phosphorus-Containing Epoxy Resin D (g) E poxy Resin 125 0136 Organic cyclic phosphorus compound HCA (216 4 (g) g) placed in a glass reaction kettle was heated and molten US 2002/0032279 A1 Mar. 14, 2002 11

EXAMPLE 8 TO 11 AND COMPARATIVE TABLE 3-continued EXAMPLE 2 Comp. 0142. In a kettle equipped with a mixer and a condenser, Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex the components according to the ratioS Shown in table 6 were Hardener A 28.2 28.0 26.5 26.5 formulated at room temperature into epoxy resin Varnish. Hardener B 31.8 Hardener C 28.3 29.5 Hardener D 53.1 TABLE 6 Hardener 18 1.2 1.O O6 O.8 0.5 O6 O6 Promoter B Compara Example Example Example Example tive 8 9 1O 11 Example 2 0140. A glass fiber fabric was impregnated in the phos Phosphorus- 105 phorus-containing epoxy resin varnish formulated above containing Epoxy Resin and then dried at 190° C. for 120 minutes, so that prepregs A(g) were formed. The glass transition temperature was measured Phosphorus- 150 by DSC (Differential Scan Calorimeter, TA 2910) (the containing temperature ranged from 50 to 250 C., temperature elevat Epoxy Resin ing rate was 20 C./minutes), and the flame retardant prop B(g) Phosphorus- 150 erty was measured by a flame test. The flame test was containing according to the method in UL 746. The prepreg was cut into Epoxy Resin 5 pieces of specimens with sizes of 12.5mmx1.3 mm. Each C(g) Specimen was Set a flame twice. If the total time for ten Phosphorus- 150 flamings was not more than 50 Seconds and each flaming containing was not more than 10 Seconds, the prepreg passed the flame Epoxy Resin test. The results are shown in Table 4. D(g) Epoxy Resin 125 4 TABLE 4 Hardener A 32.4 32.4 27.5 29.9 26.5 Hardening 2.4 O.9 O.6 O6 O.65 Ex- Ex- Ex- Ex- Ex- Ex- Ex- Compara Promoter B al- al- al- al- al- al- al- tive ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 Example 1 Average 2 to 3 0 to 1 0 to 1 2 to 3 2 to 3 1 to 2 2 to 3 1 to 2 flame time 0143. The resulting epoxy resin compositions from (sec) Example 3, 7, and 8 and Comparative Example 2 were Tg (I) 157 165 173 147 155 151 151 135 coated at a thickness of 80 um on the rough Surface of the 18 um copper foil, and dried in the oven at 170° C. The 0141 Eight pieces of prepregs were piled up. A sheet of resulting epoxy resin coated copper foils were put on both 35 um copper foil was placed on both the up and down sides, the up and down Sides of the prepregs formed from the and was laminated at 185° C. under a pressure of 25 kg/cm’ epoxy resin composition of Example 1 mentioned above, to form into a laminated entity of phosphorus-containing after being pressed at 185°C. under a pressure of 25 kg/cm epoxy resin and glass fiber fabric. The physical properties of yielding a multi-layer plate. The physical properties of Said each laminated entity were analyzed, and the results are multi-layer plates were tested, and the results are shown as shown in Table 5. Table 7.

TABLE 5 Condition Comparative Test Item and Spec Example 1 Example 4 Example 7 Example 1

Flame Test UL 94-VO ------Solder 288 C. ------Resistance spec. - 120 SCC. Peeling IPC spec. s. 11.2 11.2 10.9 11.1 Strength 81 b/in Surface spec. - 102 2.88 x 10's 1.25 x 10'S 122 x 10's 3.57 x 101 Resistance Volume spec. - 10 1.25 x 10' 0.97 x 10' 0.88 x 10' 1.06 x 10' Resistance Dielectric IPC 4.7 4.7 4.8 4.7 Constant spec. < 5.4 Dissipation - O.O2O O.O24 O.O19 Factor ("+” means: passed) US 2002/0032279 A1 Mar. 14, 2002

2. A method for producing the phosphorus-containing TABLE 7 epoxy resin according to claim 1, which comprises the Steps Compara of addition reacting 9,10-dihydro-9-Oxa-10-phosphaphenan Conditioned tive threne-10-oxide (HCA) represented by formula (C): Test Item Spec. Example 8 Example 3 Example 7 Example 2

Flame UL. 94-VO ------Test (C) Solder IPC260° C. ------Resistance spec. - 30 sec. Peeling IPC 7.6 7.4 8.0 8.4 Strength spec. 6 Ib/in (18 um) (“+” means “passed’)

1. A phosphorus-containing epoxy resin having the for with compounds containing C=O reactive group to form mula (A): a phosphorus-containing compound having an alcohol group, then condensation reacting with phenols and organic acids to yield the phosphorus-containing com (A) pound having the formula (B),

(B)

OP Epoxy-R-Arl-dh-Ar-R5 Epoxy OP-O wherein Ris selected from -O-, -NH-, -S-, R5-Arl-CH-Ar2-Rs COO-, -SO , CO-, and -CHCON< group; Ar' and Arfare independently selected from the moieties as follows: wherein R is a group selected from -OH, -NH, -SH, COOH, -SOH,-COH, or -NHCOCH; Art and Ari have the same definition of the groups described above; further reacting the resulting phosphorus-con taining compound of formula (B) either with epoxy resin having at least two epoxy groups or with an epihalohydrin to form the phosphorus-containing epoxy resin according to claim 1. 3. The method according to claim 2, wherein the equiva lent ratio of epoxy resin or epihalohydrin: phosphorus containing compound is from 100:5 to 100:150. 4. The method according to claim 3, wherein the equiva lent ratio of epoxy resin or epihalohydrin: phosphorus 7 -R ( -R8 containing compound is from 100:5 to 100:50. 5. The method according to claim 2, wherein the equiva lent ratio of epoxy resin or epihalohydrin: phosphorus VV(R), ---/(R), containing compound is from 100:5 to 100:40. 8 6. A flame-retardant resin composition which comprises: r \ R7.-(5" )n (1) the phosphorus-containing epoxy resin according to -- / claim 1, (2) a halogen-free hardener, which has a reactive hydro gen capable of reacting with the epoxy group in the R is H, Coalkyl or aryl; Ris-CH2-,-(CH4)2C-, epoxy resin, and SO,-CO-,-O-, Ris-OH, -NH, -SH, -COOH, -SOH, -COH, or -NHCOCH; m and (3) a hardening promoter. in are integers from 0 to 4, Z is an integer from 1 to 20; 7. The flame-retardant resin composition according to Epoxy- is a group containing at least one epoxy group. claim 6, wherein the halogen-free hardener of component (2) US 2002/0032279 A1 Mar. 14, 2002 is a nitrogen- or phosphorus-containing compound, having a resin not containing phosphorus which is Selected from the structure as presented by the formula (D): group consisting of epoxy resin, phenolic resin, polyester resin, polyurea resin, polyamide resin, polycyanamide resin, and the mixture thereof. (D) 9. The flame-retardant resin composition according to RHN NHR', claim 8, wherein the epoxy resin not containing phosphorus is Selected from the group consisting of bisphenol glycidyl r ether, bis(biphenylglycidyl ethers), dihydroxybenzene gly cidyl ethers, glycidyl ethers containing a nitrogen hetero R2 ring, dihydroxynaphthalene glycidyl ethers, phenolics polyglycidyl ethers, polyhydroxyphenol polyglycidyl ethers. wherein R is selected from hydrogen atom or either of the 10. The flame-retardant resin composition according to structures of formulas (E) or (E2), but at least one R' claim 8, wherein the content of the epoxy resin modified is not a hydrogen atom; with phosphorus-containing compound in the component (1) (E) R'=-CH-R), H; wherein R is phenylene, naph is from 5 to 100 wt %, based on the total weight of the epoxy thylene, or the group of the formula: resin. 11. The flame-retardant resin composition according to claim 10, wherein the content of the epoxy resin modified (R'), (R'). with phosphorus-containing compound in the component (1) is from 20 to 100 wt %, based on the total weight of the A. epoxy resin. X / \ Šy. 12. The flame-retardant resin composition according to claim 11, wherein the content of the epoxy resin modified with phosphorus-containing compound in the component (1) wherein A is O-, S-, SO , CO-, is from 5 to 100 wt %, based on the total weight of the epoxy -CH2-, -COCH-)-, or the group of the formula: CS. 13. The flame-retardant resin composition according to claim 6, wherein Said hardener is Selected from the group consisting of amines, bisphenol resins, dihydroxybenzene, —cil- Y-ch polyhydroxyphenol resins, phenolics, and anhydrides. 14. The flame-retardant resin composition according to (R'), claim 6, wherein said hardening promotor of component (3) is Selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium Salts, quaternary wherein R" is H, Co alkyl or aryl; Y is -OH, -NH2, phosphonium Salts, complex Salts of boric trifluoride, and -COOH, a is an integer of 0 to 2; x is an integer of 0 to 4; among the groups represented by R and A imidazole compounds. described above, the aryl may be substituted by one or 15. The flame-retardant resin composition according to more Substituents Selected from the hydroxy, amino, claim 6, wherein the amount of Said hardener used is from carboxy, or the C- aliphatic group; 20 to 140 based on the reactive hydrogen equivalent weight, the reactive hydrogen equivalent weight of the epoxy resin (E2) being 100. 16. The flame-retardant resin composition according to claim 15, wherein the amount of Said hardener used is from 50 to 95 based on the reactive hydrogen equivalent weight, O the reactive hydrogen equivalent weight of the epoxy resin being 100. 17. The flame-retardant resin composition according to -at-e-cut O claim 6, wherein the content of Said hardening promoter is from 50 to 50,000 ppm of the total weight of the epoxy resin composition. 18. The flame-retardant resin composition according to claim 17, wherein the content of Said hardening promoter is wherein R is -NHR', C alkyl or aryl; n is an integer from 100 to 30,000 ppm of the total weight of the epoxy of 0-20; but at least one R' is not a hydrogen atom; the resin composition. definitions of R and n in formula (E) are respectively 19. The flame-retardant resin composition according to the same as those in the above formula (E). claim 18, wherein the content of Said hardening promoter is 8. The flame-retardant resin composition according to from 500 to 2000 ppm of the total weight of the epoxy resin claim 6, wherein the component (1) further includes epoxy composition. US 2002/0032279 A1 Mar. 14, 2002 14

20. The flame-retardant resin composition according to 21. Ahardened article, which is obtained by hardening the any of claims 6 to 19, which is used in the manufacture of flame-retardant resin composition according to any of claims adhesive plates, composite materials, laminated plates, 6 to 20 at the temperature range from 20 to 350° C. printed circuit boards, Substrates for build-up process, cop per foil adhesives, and IC packages. k k k k k