TWI259188B - Flame retardant epoxy resin composition - Google Patents

Abstract

The present invention is related to a flame retardant epoxy resin composition, which is characterized by a side-chained phosphorous-containing epoxy resin expressed as formula (I), in which each symbol is defined as follows. The resin composition can also comprise (1) an epoxy resin excluding the side-chained phosphorous-containing epoxy resin expressed as formula (I); (2) a curing agent; (3) a curing accelerator; (4) an inorganic filling agent; and (5) an additive. The resin composition doesn't contain halogen without adding flame retardant agent, so as to exhibit flame retardancy and high heat resistance achieving the UL 94V-0 standard. The composition is especially suitable for being used as a semiconductor packaging materials and manufacturing binding sheets, composite materials, laminate plates, printed circuit board, substrate for build-up and copper foil.

Description

259188

V. Description of the invention (1) [Invention field]

I. Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed. b This invention discloses a composition comprising a flame retardant side chain type dish-containing epoxy resin. The resin composition of the present invention does not contain 3 hexahydrate and bismuth oxide: hazardous substances, and has a flame retardant property of UL94V.0 and high heat resistance. The resin composition of the present invention can be applied to ^ k ' of electronic semi-finished, crucible packaging materials and obtains good moldability and reliability. [Background of the Invention] At present, in terms of cost and product characteristics, an epoxy resin composition is generally used as a packaging material for a semiconductor device or the like. In order to ensure the safety of the electronic components of these semiconductors, the epoxy resin composition used as the encapsulating material is required to comply with UL's flame retardant specifications. Generally, such an epoxy resin composition is used as a flame retardant additive by adding a compound containing a halogen (9) such as an epoxy resin containing iS) and antimony trioxide. Meets the requirements of UL flame retardant specifications. The resin composition generally used is obtained by adding a halogen-containing compound, particularly a bromine-containing epoxy resin and a hardener, and blending a flame retardant auxiliary such as diterpenoid in order to form the resin composition. The material meets the stringent requirements for flame retardant properties (eg UL·94V-0 rating). Generally, the content of flame retardant in the epoxy resin needs to be as high as 17% to 21% of the bromine content, and in combination with ruthenium pentoxide or other flame retardant, the UL 94 V-0 standard can be achieved. However, the current use of halogen-containing epoxy resins or antimony trioxides can cause harm to humans. First, antimony trioxide has been classified as a carcinogen, which has a very adverse effect on human health. On the other hand, in addition to the bromine, there are corrosive bromine radicals and brominated paper iII. Home Standard (CI^_4 Specification (2)G χ 29 )--- 16334 (Please read the notes on the back and fill out this page)

2 1259188 V. INSTRUCTIONS (Hydrogen, high bromine-containing aryl compounds combined with desertified dioxins, and serious: highly virulent desertification mites and sputum, seeking m ^ affecting human health and environment It is an urgent task for Shanghai to reinforce the new flame retardant materials to improve the current semiconductor sealing materials. The pollution caused by the blue grease and environmental protection are based on the dish compound as a new one. The generation has a ring that has been extensively studied and applied. Difficult ^ Yes, such as the use of red disc or Dendrobium organic compounds (for example: r laugh | & ~ - base phosphoric acid, trityl phosphate vinegar, Phosphate Temple) replaces dentate compounds as yttrium, yttrium, ytterbium, yttrium, to improve the combustion characteristics of materials or hardened resins. However, it is limited to add these compounds to the tree For the flame retardant efficiency of these compounds, it is necessary to increase the amount of the added port, and the high drift line (, _) caused by the low molecular weight of these compounds, the characteristics of the resin composition: such as electrical properties, strength, etc. The adverse effects are caused by practical problems. For example, as disclosed in the Republic of China Patent No. 339353, the use of red lining as a flame retardant replaces the flame retardant containing halogen and telluride. However, such materials undergo high temperatures. After the tomb is boiled, the red phosphorus will be hydrolyzed and changed. At the same time, the operation process is dangerous: it also has a bad influence on the process and the finished product. In recent years, with the consideration of environmental protection and safety, it has gradually begun to try to use reactive flame retardants. And began to use the epoxy resin to replace the brominated epoxy resin, so that the resin composition has improved flame retardant properties, such as Japanese Patent No. 9_235449, that is, the use of phosphorus-containing resin instead of bromine and recorded matter In the burning process, the resin composition does not produce dioxin due to the inclusion of the sputum; in the case of the patent of U.S. Patent No. 5, 3, 7, 6, 5, Net/paper scale applicable to China National Standard (CNS) A4 specification (210x 297 mm) ^- with 16334 2 1259188

V. INSTRUCTIONS (3) The Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative printed a laminate made of epoxy tartarate and a nitrogen-containing hardener composition, which is not easy to achieve UL 94V-0 combustion. Standards, a plurality of compositions containing a phosphate ester epoxy resin must be added to increase the content of ruthenium; in the patents of U.S. Patent Nos. 4,973,631 and 5,086,156, three active hydrogen substituents (e.g., amine groups) are used alone. Hydrocarbyl phosphine oxides or other amine hardeners used to harden epoxy resins. In this hardening method, sarcophagus is introduced into the resin, but the content of scales in the composition is low and the required flame retardant standard cannot be achieved. . Since the addition type or the reactive type phosphorus-containing substance has a low disc content, the flame retarding effect is not good, and if the resin composition has a flame retardant property conforming to the standard, a large amount of such a content is required to be added to the formulation. Phosphorus or a variety of phosphorus-containing compounds, as a result of the exclusion of the amount of epoxy resin and hardener added 'to make the processing conditions of the product difficult to control, resulting in reduced product quality. Generally used to replace halogen-containing and antimony compounds, most of which are nitrogen-containing and phosphorus-containing materials. 'The most commonly used nitrogen-containing substances are melamine, dicyandiamide (DICY), cyanate esters containing triazine rings. And the phosphorus-containing substance used is a functional compound-containing compound or a non-reactive type stone-containing compound, wherein the 'non-reactive type scaly compound has poor heat resistance and is less suitable for use. The highly reactive composition of the high-heat composition is highly thermally stable due to the bonding with other molecules, so the 'reactive phosphorus-containing compound is gradually becoming the mainstream in the future. Among the reactive wall-containing compounds today, the most common user is a linear type of phosphorus-containing compound. This reactive linear phosphatide contains 16334 (please read the back of the note? Fill in this page)

3 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1259188 A7 -----Η_____ V. Invention description (4) Often due to the _0_Ρ_0_ key on its main chain, its heat resistance is more halogen or not 3 i The composition of the oxy-resin is poor; on the other hand, the composition of the flame-retardant resin composition has a linear type of compound or a non-reactive type of compound, and its application is more than the current epoxy. The resin composition is inferior in workability. The resin composition having a side chain type scaly epoxy resin disclosed in the present invention is characterized in that a substance having a dish at a side chain position is directly added to the composition to obtain a current epoxy resin composition containing a side chain molecule. The group will reduce the fluidity of the phosphorus-containing epoxy resin compound, and its molecular stability is high at high temperatures, and the heat resistance is also high', and its difference in sanitization with the current air-containing epoxy tree is small. The present invention is based on the above, and improves the shortcomings of the prior art, and aims to improve the basic properties of electric and mechanical and reduce the cost, and reveals a novel phosphorus-containing epoxy resin composition for manufacturing a flame retardant effect. And a semiconductor package material with excellent heat resistance. [Summary of the Invention] The present invention provides a resin composition having a side chain type phosphorus-containing epoxy resin represented by the formula (I): < The paper scale is applicable to the Chinese national standard ((:?45)^_格(210 x 297 mm 16334 (please read the notes on the back and fill out this page)

4 1259188 A7 B7 V. Description of invention (5

(I) Printed by the Ministry of Economic Affairs, the Ministry of Finance, and the Consumers' Cooperatives. The symbols are as follows. 4 The resin composition is halogen-free and has a flame retardant property up to UL 94V-0 and high heat resistance without additional addition of a flame retardant. The resin composition provided by the present invention comprises, in addition to the side chain type disk-containing epoxy resin represented by the formula (j;), an epoxy resin other than the side bond type disk-containing epoxy resin represented by the formula (1); (2) a hardener; (3) a hardening accelerator; an inorganic filler; and (5) an additive. In the resin composition of the present invention, the side chain type phosphorus-containing epoxy resin means a phosphorus-containing epoxy resin having reactivity at a side chain position of the resin; the coating of the resin is caused by a reaction having a monofunctional group Hca (6-hydroxy-di-bromo-(c,e)(l,2)-oxaphosphorus) is reacted with a reactive aldehyde to carry out a condensation reaction, and finally, with epichlorohydrin or ring The oxygen-lipid reaction is carried out to prepare a phosphorus-containing epoxy resin having reactivity in a side chain. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame retardant disk-containing epoxy resin composition, the composition of which is characterized by having the side of the following formula (1) _gf $ specification (2) 〇 x 297 Dong:—Μ... 衣 曰 5 16334 (Please read the phonetic on the back? Please fill out this page again) ^OJ· n —9 ϋ .11 nnn I nn I n i_l n I inn ϋ ϋ I ϋ I ϋ ϋ ϋ ϋ ϋ I , 1259188 A7 ----- ___B7_____ V. Description of invention (6 )

In the formula U), 'a is an integer from 1 to 1 ;; b is an integer from 〇 to 1 ;; a stilbene group; and Arl and Ar2 are selected from the groups represented by the formulae (1 a) and (I b) :

or

(where m and n are integers from 〇 to 4; Ri is j^c alkyl); and X is a group represented by formula (I c): Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 0H - (O -CH2-CH-CH2-OM-) (Ic) [wherein, y is an integer from 0 to 20, μΑΓΤ is a group represented by a horse (1 a), or is selected from the formulae (E1), (E 2) Group consisting of: (E1) The group shown in the following formula: This paper size thorn cap 0 standard (CNS) A4 specification (210 X 297 mm 16334 (please read the back note first and then fill in this page) )

1259188

V. Description of the invention (

(Ε1) In the formula (la), R' is Η or CH3; Α is a chemical bond, _〇_, _s S〇2_, _C〇-, _CIV, -C(CH3)2- or a group represented by the following formula : -ch2-<Q>-Ch2 or (Ε2) has a novolak epoxy resin of the following formula: (Please read the notes on the back and fill out this page)

In the formula (Ε2), ' Ri is as defined above; d is an integer from 〇 to 6; r2 and R6 are independently Η or a group represented by the following formula: (Ε2) Ministry of Economic Affairs, Intellectual Property Office, employee consumption cooperation

(wherein R1 is as defined above)]. In the formula (I), the CK4 alkyl group means an alkyl group having from 丨 to 4 carbon atoms, and the example thereof may be an alkyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or an isobutyl group. , third butyl, and the like. _In the resin composition of the present invention, the side chain type sarcophagus ring of the formula (I) is applicable to the paper size (CNS) A4 specification (21G χ 297 -------1 7 16334)

!259188

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Invention Description (9) is bisphenol F), bis(4,phenyl) maple (also known as bisphenol S), bis(4-hydroxyphenyl) (4_Phenyl)nonylbenzene, 4,4,_dibiphenyl, 4,4,·di-diyl', M tetramethyl ear, benzene, 4,4-di-diphenyl ether, ^二经基_ '3'3' fluorenyl_1, 1-spirodioxan and 1,3,3-trimethyl small (4-hydroxyphenyl)-1 -printed-6-drunk; The two sides of the Saiping are called to raise XK, such as tetrahydroxyphenylethane and naphthol·A®^/acid tree, and expectant resin members, such as bismuth acid resin, 酉分芳f f, naphthol aralkyl and phenol-bicyclic diene copolymer resin; aliphatic and square "Ya Yue female class" 士 乙 ethylene diamine, propylene diamine, hexamethylene diamine, aniline , Μ · a basic base of ketone _ eight), 4, 4, 2, 2, bis (4,4, diaminophenyl propyl, m-phenyl-monomethylamine, p-xylylenediamine, 1 , 2-diaminocyclohexene and aniline aralkyl resins; aminophenols such as m-, phenol, p-, phenol, 2-(4-aminophenyl)-2-(4, Phenyl) And cardinyl phenyl _4' by phenylmethane, etc.; carboxylic acids, such as citric acid, isophthalic acid, citric acid, tetra: citric acid, hexahydro phthalic acid, - henry, Ί ^ ...酉夂 and L3-dicarboxycyclohexane; and the like, and hydroxycarboxylic acids and the like, such as salicylic acid and 4-hydroxybenzoic acid. In the resin composition of the present invention, the epoxy resin as the component (1) is glycidyl ether. Preferably, examples of the monomer include: bisphenol glycidyl ether, boring knife, hydrazine glycerol, benzodiazepine glycidyl bond, glycidyl ether of nitrogen ring, glycidyl ether of monohydroxynaphthyl , phenolic glycidyl ether, polyglycol glycidyl ether, etc. Examples of soil bisphenol glycidyl ether include: bisphenol A glycidyl ether, cone-aged water glycerin, double-fold AD glycidyl bond, double hope (10) water Glycerin ^ Tetramethyl bisphenol A glycidyl ether, tetradecyl bisphenol F glycidyl ether, tetramethyl bis-pans AD glycidyl ether, tetramethyl bisphenol S glycidol This paper scale applies to China national standard ^fS )A4 Specifications (2)G χNaughty Love Ding 3 (Please read the notes on the back and fill out this page)

Order ----------Line I nn I · 16334 9 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Ϊ 259188 V. Invention Description (η In the tree composition of the present invention, the side chain type includes The content of the epoxidized person is preferably from 3 to 1% by weight based on the total content of the epoxy resin: more preferably from ::10 to 8% by weight. If the content ratio is less than three. In the resin composition of the present invention, one or more of the components (7) having a hardening agent which reacts with an epoxy group may be various (four) resins including nitrogen. Phosphorus compounds and other halogen-free compounds. The ten or two bismuth and phosphorus resin hardeners have the structure shown by the following formula (11):

(Π), wherein Rlc!-6 alkyl, phenyl or -NH R4 ; R4 is a hydrogen atom, a group of the formula (na) or (II b), and the condition is at least _ han 4 For the scorpion;

_(CHrR5)nH (Ha) In the formula (Π a), η is an integer from 〇 to 20; R5 is a group represented by an extended aryl group or a formula Uai)

(na-1) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 11 16334 1259188

V. INSTRUCTION DESCRIPTION (I2) In the formula (Formula Ua-1), R7 is Η or CH3; A is a chemical bond, _〇_, _s_, _CH2-, -C(CH3)2- or the following formula -SO--, _co The group shown: -ch2 ch2 or

The above aromatic groups represented by R and A may be substituted by _ or a plurality of substituents selected from the group consisting of a hydroxyl group, an amine group, a thio group, and a c i -6 alkyl group]; —(CH2.R5-CH2)w

(nb) (Please read the phonetic transcription on the back side and then fill out this page.) The Ministry of Economic Affairs, Intellectual Property, and the Consumer Protection Agency, Printed (Π b), R5 and n are as defined above. In the formula (Π), examples of the aryl group may be a phenyl group, a naphthyl group or the like. The phenol resin used in the resin composition of the present invention can be obtained by reacting a phenol compound having an aldehyde (generally formaldehyde) under the presence of an acid catalyst. The phenols which can be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol and p-ethylphenol. In the resin composition of the present invention, one or more hardeners which have active hydrogen to react with an epoxy group may be used as the component (2), and other halogen-free compounds may be used, and examples thereof include: amines and benzene. Phenol, bisphenol resin, polyhydric phenol resin, phenolic acid, acid anhydride, and the like. Examples of the amines include dicyandiamide, dicyandiamide, methylenediphenylamine, diaminodiphenylmethane, cesium adipate, strontium isotonic acid, and the like. Examples of benzene-prospective include: · benzophenone, hydroquinone, isobutyl to the paper scale applicable to China National Standard (CNS) A4 specifications (2) 297 297 public) ------- 12 16334 ί - - 丨 丨丨 丨丨 n n ϋ n ϋ A7 1259188 V, invention description (13) benzenediol and so on. Examples of the double resin include: containing the formula H〇_ph_X-Ph-〇H (where Ph represents a phenyl group, χ = a chemical bond, _CH2 — _C (CH^_, _〇_, _s_, -CO-, - Compounds shown by SCV), for example: bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol AD, tetramethyl bisphenol s, tetramethyl bisphenol A, tetradecyl double Phenol, 4,, 4'-biphenol, 3,3,-dimethyl-4,4,-biphenol, 3,3'5,5'-tetramethyl-4,4,biphenol, etc. Examples of poly(hydroxyphenol) resins include: quinone (4-hydroxyphenyl) decane, stilbene (4-phenylphenyl) ethane, stilbene (4-hydroxyphenyl) propane, ginseng-hydroxyphenyl Butane, ginseng (3.methyl-4-hydroxyphenyl)methane, ginseng (3, dimethyl-4-hydroxyphenyl) decane, hydrazine (4-hydroxyphenyl) ethane, hydrazine (3) , 5_dimercapto_4_hydroxyphenyl)ethane, and the like. Examples of the acid include a phenol formaldehyde condensate, a phenol phenol aldehyde condensate, a bisphenol A phenol aldehyde condensate, a biscyclopentene phenol aldehyde condensate, and the like. Examples of the acid anhydrides include: phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, decyl hexahydrophthalic anhydride, pyromellitic anhydride, diphenylmethyltetracarboxylic anhydride, 3, 3, , 4,4,_biphenyltetracarboxylic anhydride, bis, cardiocarboxyphenyl ether anhydride, bis(3,4-dicarboxyphenyl)decanoic anhydride, 2,2-bis(3,4-dicarboxyl Phenyl) propane anhydride or the like. In the resin composition of the present invention, the hardener is added in an amount equivalent to the epoxy equivalent of the epoxy resin and the reactive hydrogen equivalent of each hardener, and the epoxy equivalent of the asphalt resin to the hardener A suitable equivalent ratio of the reactive hydrogen equivalent is from 100:50 to 100:150, preferably from 1 〇〇:6 〇 to 1 〇〇:140, and more preferably from 100:70 to 1 〇〇:130. (Please read the notes on the back and fill out this page.) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives ·* · 一\; — — — — — — — — — — — —

13 16334 [259188

5. Description of the Invention (Μ) Examples of the hardening accelerator used as the component (3) in the resin composition of the present invention include: tertiary amine, tertiary phosphine, quarter salt, quaternary salt, boron trifluoride Compound, lithium compound, hydrazine, 8 diazabicyclo ring (please read the back of this note and fill out this page) One coat (5,4,0) undecene-7-(DBU) undecene compound , an imidazole compound or a mixture thereof. Examples of tertiary amines include: triethylamine, tributylamine, dimethylphenylamine, diethylphenylamine, α-methylbenzyldimethylamine, dimethylamine ethanol, ginseng (Ν, Ν-dimethyl.aminomethyl), ν, ν_dimethylaminomethyl, etc. Examples of the tertiary phosphine include triphenylphosphine and the like. Examples of the quaternary ammonium salt include: tetramethylammonium chloride, tetramethylsulfate, tetradecyl ammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium moth, four Butyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium iodide, Triethylphenethylammonium chloride, triethylphenethylammonium bromide, triethylphenethylammonium iodide, and the like. Examples of seasonal salt samples include: tetrabutyl sulphate chloride, tetrabutyl sulphate desertification economic department, intellectual property bureau employee consumption cooperative printing, tetrabutyl sulphate iodide, tetrabutyl sulphate acetate , tetraphenyl squaride chloride, tetraphenyl sulphate bromide, tetraphenyl sulphate, ethyl diphenyl sulphate, ethyl triphenyl sulphate, ethyl triphenyl sulphide, Ethyl triphenyl sulphate acetate acetate, ethyl triphenyl sulphate acetate acid complex, propyl triphenyl sulphate chloride, propyl triphenyl sulfonium bromide, propyl three Phenyl sulphide iodide, butyl triphenyl squaride chloride, butyl triphenyl squarate bromide, butyl triphenyl squaride iodide, and the like. Examples of oral rice bran compounds include: 2-methylimidazole, 2-ethylimidazole Table paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 public meals) 14 16334 1259188

V. Description of the invention (15 2 -phenyl miso, 4 _ ψ A. Sit, 2-styl-methyl bis-salt, 4-ethyl succinyl, 2-phenyl-4-methyl-hydroxymethyl Imidazole, i-diazole, oxazole, 2-ethyl Imethylimidazole, 2-ethylidene, carbamazepine, etc. 1-ethyl-4-methylpyrene, and 2-stylyl-5-di-perylene The form of the hardening accelerator composition is used. Two or more kinds of compounds are mixed, especially two... preferably a tertiary amine, a tertiary phosphine, and a hydrazine-methylbenzamine, triphenylphosphine, 2- Mercaptoimidazole, 2 meryl imidazole, 2-ethylamine 4 Tianbo 1 soil-methylimidazole, or a mixture thereof. The resin composition of the rabbit Ming, ^ t the amount of the hardening accelerator added in the wind, in private The total amount of the ruthenium composition is from 0. 01 to 5 weight i ° / 〇, preferably from 0. 05 to 3 weight. The addition amount of the right hardening accelerator exceeds 5% by weight, which can shorten the reaction time. The electrical properties and anti-thirsty water absorption properties required for product formation and subsequent application have an adverse effect; if the amount of addition is insufficient, the reaction rate may not be effectively reacted. In the resin composition of the present invention, the inorganic filler of the component (4) is packaged. Oxygen Huayu powder (including spherical and angular molten cerium oxide, crystalline dioxin: lanthanum, etc.), stone (four) powder, talcum powder, oxidized powder, oxidized powder, anaerobic , the nitrogen compound, the side acid acid, etc. The average particle diameter of the j filler is preferably 丨 to 4 〇 # m, and if the average particle diameter is less than (5), the viscosity of the resin composition is increased to decrease the fluidity; If it exceeds 4 #m, it will cause uneven distribution of resin and filler in the composition, which will cause variation in physical properties and cause resin overflow during package molding. In addition, the maximum particle size of the filler should be less than 1 50 // m to avoid causing poor filling between small narrow runners or slits. ^张和(四)用r _家标准(CNk)A4规袼(10)x 297 公爱) % Intersexual slow 15 16334 (Please Read the phonetic transcription on the back first? Then fill out this page. Book i • i I nn - 丨 !!! 1259188

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (w) The inorganic filler can be thought of, the object # <# or a combination of two or more in a mixed use. Among them, those of - Μ ^ ^ are angular molten cerium oxide, crystalline emulsified cerium, and angular melting. - Mixing of bismuth telluride and spherical cerium oxide In the resin composition of the present invention, the amount of the filler added to the ^ ^ Θ Θ 祛 , , , , , , , , , 50 50 50 50 50 50 50 50 50 50 Dan. / , 0 / ^ 0 heavy / 〇, preferably 55 to 87 weight agent added low 5G weight ^ more resin content = resin (four) bad; if the filler added $ higher than 90% by weight The rule will increase the viscosity of the composition and reduce the fluidity. ‘, as usual. The hardening accelerator is added in an amount such that the hardening time of the resin is in the range of 30 to 500 sec / 171 t, and the amount of the viscosity is preferably in the range of 2 Torr to 500 cp / 25 ° C. . In the resin composition of the present invention, examples of the additive of the component (5) include a decane coupling agent, a colorant (carbon black and iron oxide), a releasing agent, a low stress additive and the like. Examples of the coupling agent used in the present invention include: vinyl methoxymethoxine, vinyl triethoxy decane, N-(2-aminomethyl)_3_aminopropyl-mercapto-dioxanthene' N -(2-Aminoethyl)-3-aminopropyl-trimethoxy decane, 3-aminopropyl-diethoxy decane, 3-anilinopropyl-triethoxy decane, 3-methoxypropylpropyl- Trioxoxane, 3-epoxypropylpropyl-indenyl-dimethoxyhydrazine, 2(3,epoxycyclohexyl)ethyl-trioxoxalate, 3-methylpropoxy Propyl-trioxoxanes and 3-hydrothiopropyl-trioxoxanes. The present invention will be described in detail below with reference to specific examples, and it should be understood that the paper scales are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 16 16334 (please read the phonetic transcription on the back side and then fill out this page) 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Synthesis Example, Examples and Comparative Examples] The components used in the synthesis examples and examples are detailed below. · Epoxy Resin A ·· represents a cresol-aldehyde sold by the Changchun Synthetic Resin Factory under the trade name CNE200ELB. The polyglycidyl ether of the condensate has an epoxy equivalent of 200 to 220 g/eq and a hydrolyzable chlorine of 2 〇〇 ppm or less. Epoxy Resin B · Represents 3,3,5,5,_tetramethyl·4,4, phenol sold by Yuka Shell Epoxy Κ·Κ·, sold under the trade name ΥΧ4000Η, with an epoxy equivalent of 180 Up to 195 g/eq. Epoxy resin C _· represents the diglycidyl ether of tetrabromobisphenol A under the trade name BEB350, which has an epoxy equivalent of 330 to 350 g/eq and a bromine content of 23 to 26 by weight. Wt%. Wire Hardener A · Represented by Changchun Synthetic Resin Factory under the trade name PF-5110 with an active hydrogen equivalent of between 1 and 5 〇g/eq. Hardening accelerator A: represents triphenylphosphine. Hardening accelerator B: represents 2-methylimidazole (2MI). Intellectual Property Intelligence Bureau Member X Consumer Cooperative Printed Free Example 1: Manufacturing Step of Phosphorus-Containing Epoxy Resin D (1): 216 g of Organic Cyclic Phosphorus Compound HCA (6-Hydroxy-Dibenzo-(c,e) (1,2)-oxaphosphorus) and 216 g of toluene were placed in a glass reaction dad to heat and dissolve and stir. When the temperature reached 110 ° C, 112 § of 4_ mercaptoic acid was added and allowed to react for 2 hours. After the reaction mixture was cooled to room temperature, it was filtered, and the filtrate was dried to give an organic cyclic phosphorus compound (a) having a melting point of 212 °C. I paper size is applicable to China National Standard (CNS) A4 specification (2) Qχ 297 public) 17 16334 Α7 Β7 1259188 V. Invention description (18) Step (2)· 338g of organic ring-shaped dish compound (a) and Stupid's placed in a glass reactor to dissolve and stir. When the temperature reached 丨i 〇 °C, 94 g of phenol and 3.4 g of p-mercaptosulfonic acid were added and allowed to react for 2 hours. After the reaction composition was cooled to room temperature, it was filtered, and dried to give an organic cyclic compound (b) having a melting point of 294 °C. Step (3): 414 g of the organic cyclic scaly compound (b) and the chloropropane were placed in a glass reactor and heated and stirred. When the temperature reached 5: °, 153.5 g of a 49.5% aqueous sodium hydroxide solution was added and allowed to react for $hour. After the above reaction composition was vacuum-heated to recover the raw material epoxidized propane to a temperature of 155 ° C, an organic solvent and water were added, and the organic solvent in the resin liquid was recovered by draining water to form 5 18 g of a novel phosphorus-containing epoxy resin ruthenium. The epoxy resin D contained in the above reaction had an epoxy equivalent of 288 (g/eq) and a softening point of 85 °C. Production of gold straight phosphorus-containing epoxy resin E Step (1): In the same manner as in Synthesis Example 1, a reaction was carried out by substituting 1 〇 8 g of o-cresol for phenol. After the reaction composition was cooled to room temperature, it was filtered, and the filtrate was dried to give an organic cyclic phosphorus compound (c) having a melting point of 245. . . ', ......, step (2): 428 g of the organic cyclic phosphorus compound (c) and 925 g of epichlorohydrin are reacted in the same manner as in the synthesis example i to generate a novel phosphorus-containing epoxy resin of 539= Resin E. The novel scaly epoxy resin E obtained by the above reaction has an epoxy equivalent of 3 Å (g/eq) and a softening point of 95. Synthesis of a hardener B with a dish and nitrogen epoxy resin _ τ _ home standard (CNS) A4 specifications (2) 〇χ move 16334 (please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing _·-------- order- --------Line 丨®----------IL丨丨一丨nnn on 18 1259188

Ministry of Economic Affairs, Zhihui, Fiscal Production Bureau, staff, consumption, cooperation, printing, printing, printing, printing, printing, printing, printing, printing, printing, printing I, electric mixer and mixing rod, nitrogen inlet, thermocouple, water-cooled condenser, addition funnel, 3_ml five-neck glass reactor, put phenol 1410 g (15 m), 92% polyoxymethylene 244.7 g (7.5 moles), benzene guanine 337 grams (1.8 moles), hca grams (1.2 moles) and oxalic acid! ι 2 g, after melting, vacuuming the above materials, then introducing nitrogen gas and evacuating. The temperature was raised to 1 Torr to u〇t:, the reaction was carried out for 3 hours, and the temperature was further raised to 120 to 125 ° C to carry out a reaction for 2 hours. After the end of the reaction, the unreacted phenol and the reaction condensation water were slowly distilled off under normal pressure, and finally kept at 18 Torr under vacuum for 1 hour. The resulting product was an epoxy resin hardener B containing phosphorus and nitrogen. The softening point was analyzed to be 161 ° C, the theoretical nitrogen content was 1 〇 % wt%, the phosphorus content was 2.93 wt%, and the active hydrogen equivalent was 2 i 〇 g / eq. For the epoxy equivalent (EEW, Ep〇xy Weight), varnish viscosity (Visc〇sity), softening point (s〇ftening (10) plus) used in this article, test according to the following test method: (1) Epoxy equivalent: The epoxy resin was dissolved in a solvent of chlorobenzene··chloroform: 1, titrated with hydrogen bromide/glacial acetic acid, and crystal violet as an indicator, measured according to the method of ASTM D 1 652. (2) Viscosity: Place the phosphorus-containing epoxy resin varnish in a 25-well bath at a temperature of 25 °C using a Brookfield viscometer. (3) Softening point: measured by the method of ring and ball. (Examples and Comparative Examples) The compositions of the present invention were prepared in the following examples: Example 1 Yuxi ft tree month A - 12.34 parts by weight This paper size is applicable _ 冢 standard (CNS) A4 size (10) χ 297 19 16334 (Please read the note on the back and fill out this page) ί - Line-·丨丨1259188 A7 B7 Ministry of Economic Affairs wisdom j. Bureau employee consumption cooperative printing 5, invention description (2〇) ring Oxygen Resin D Hardener A Hardening Accelerator A 矽 Coupling agent cerium oxide carbon black Brazilian brown wax The above composition is first mixed with a mixer _ and a 3-axis roller, and then pulverized after cooling.遂 Obtain an epoxy resin composition that can be packaged in a semiconductor package. The results of the experiments are shown in Tables. Each of the raw material components of Examples 2 to 7 is shown in Table 1, and the results are shown in Tables 1 and 2. Comparative Examples 1 to 3: The results of the respective raw material components shown in Table 1 are not shown in Tables 1 and 2. The superiority is obtained by the following analytical methods. (1) Spiral flow: According to the measurement method of EMMM-66, the composition fluidity was measured under 丨75 and 7 〇Kg/cm2i. (2) Flame retardancy: A test piece of 5 inches long, 5 inches wide and 1/8 inch thick, and then flame retardant. Applicable for each burning time and paper size (CNSM4 size (10)X 297 public) ------ ----4.00 parts by weight----7 · 80 parts by weight----〇· 2 6 Parts by weight ---- 60 parts by weight - 74.00 parts by weight - 〇 · 4 0 parts by weight - 60 parts by weight, after mixing, 95 ° The double of C was manufactured in the same manner as in Example 1 to produce the characteristics of each composition in the same manner as in Example 1, and I. 20 16334 f. Read the contents of the back > i sound" and fill in the page. I - * ^----------^ —^w---------------- ϋ nn —9 ϋ I f - 1259188 A7 V. Description of invention (21 ) More than 50 seconds, the maximum time is no more than 1 second, that is, the coat is not flammable. The results are shown in Tables 1 and 2. (3) Hygroscopicity: A circular test piece having a diameter of 25 mm and a thickness of 5 mm was subjected to boiling in a boiling water for 24 hours, and then the water absorption weight increase rate was tested. (4) Reflow heat resistance: The molded 18-pin double-row pin is packaged at 175 ° C (18 LD_ PDIP) and hardened after 175 ° C for 4 hours, after treatment at 85 r / 85% for 72 hours. Continuously heat at temperature 24 (TC soldering furnace three times) each time for 10 seconds, check whether the appearance of cracks. (Please read the phonetic on the back? Please fill out this page again) Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 21 16334 *~________^----------- Line — ------------------------ 1259188 A7 B7 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions (22 Table Implementation, Implementation, Implementation, Implementation, Implementation, Comparison, Comparison, Example 1, Example 2, Example, 3, 4, 5, 6, 7, 1, 2, 3, Epoxy A 12.34 12.2 - 12.34 - 6.2 6.12 15.84 A 12.84 Epoxy Resin B - - 12.34 - 12.2 6.14 6.1 Hua 15.2 Epoxy Resin C - - - - - - ~ Mine - 2.0 Epoxy Resin D 4.0 4.0 4.0 - - 2.0 2.0 0.5 - Epoxy E - - - 4.0 4.0 2.0 2.0 bismuth trioxide - - - - - - - - 1.5 Triphenyl phosphate - - - - - - - - 3.0 Hardener A 7.8 7.1 7.8 7 .8 7.1 7.8 7.0 8.1 8.1 7.8 Hardener B - 1.0 - - 1.0 - 1.0 - Hardening accelerator A 0.26 0.13 0.26 0.26 0.13 0.26 0.13 0.26 0.13 0.26 Hardening accelerator B - 0.05 - - 0.05 - 0.05 - 0.05 One stone eve coupling agent 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Fused cerium oxide 74.0 74.0 74.0 74.0 74.0 74.0 74.0 74.0 74.0 74.0 Carbon black 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Brazil brown wax —==—====== 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Spiral flow 75 72 (£S)_ 80 75 75 75 72 78 60 65 Flame resistance UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V -0 V-1 V-0 V-0 Hygroscopicity (%) 0.27 0.28 0.27 0.27 0.28 0.27 0.28 0.25 0.37 0.24 Reflow heat resistance 0/10 0/10 0/10 0/10 0/10 0/10 0 /10 2/10 3/10 2/10 Remarks Fluidity does not contain bromine formula (please read the notes on the back and fill out this page) -nnnn ϋ ϋ 1 OJ tmmmmm la— *_ϋ ·ϋ n 丨· This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 22 16334 1259188

Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printing 23 According to the above knowledge, we added flame retardant phosphorus-containing epoxy trees D and E to Examples 1 to 7, and used different epoxy resins and hardening accelerators. It is made up of a flame retardant resin composition. Compared with the non-reactive type of life-saving agent added in Comparative Example 2, and the addition of bromine-containing and non-flammable substances in the comparative example 3, there is a considerable effect on the burning property. In the case of fluidity, the pass (10) test is performed; and in the reflow soldering property, the resin composition of the reactive type flame-retardant phosphorus-containing epoxy resin is added to have a good result. In Comparative Example 1, the addition of the flame-retardant phosphorus-containing epoxy resin compound accounted for less than 5% by weight of all the epoxy resin content, and the test was not passed, and the heat resistance of the reflow was also deteriorated. Comparative Example 2 is an epoxy resin resin composition prepared by adding a non-reactive flame retardant triphenyl phosphate. Although the 94ULV training test passed, the fluidity tends to be unfavorable after the incombustibility, and the composition is sucked. Both wetness and heat resistance in soldering are poor. Comparative Example 3 is a conventionally contained indifferent and recorded incombustible substance, which is excluded due to the added amount: the amount of fat added, and the fluidity tends to be unfavorable when the flame retardancy is reached, and the reflow resistance is also added to the flame retardant inclusion. The resin composition of the resin compound is in the Chinese country. It is difficult to use 16334 it------ (please read the phonetic on the back? Please fill out this page again) - Line 丨▲ 1259188 A7 ------ V. Invention Description (24) ^ The material is connected to the side chain type epoxy resin yarn to the composition, without the need to add a toxic flame retardant containing elements such as a functional element or a recording compound, and has a UL94V-0 standard. It is characterized by its flame retardant properties and high heat resistance. It also has the characteristics of fluidity and hygroscopicity. It is especially suitable for use as a semiconductor seal. Please read the phonetic transcription on the back first. Matters to fill out this page} ------- 丨 - - - 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨

16334 24

Claims (1)

1259188 ; γι -...ί .,...; Factory............:... _;__ Η3 ang y 1 i 1 6 b 5 j Patent application for patent scope amendment (95 years 5 A flame retardant epoxy resin composition characterized by having 10 to 80% by weight of a side chain type phosphorus-containing epoxy resin represented by the following formula (1) based on the total weight of the epoxy resin: (I) In the formula (1), a is an integer of 1 to 1 ;; ] 3 is an integer of 〇 to 1 ;; the ruler is an arsenic group; and Ar1 and Ar2 are selected from the formulas (a) and (jb) Group: Ministry of Economic Affairs Central Bureau of Standards Staff Welfare Committee prints (Rl)m (R1)n or (1 a) (I b) (where m and n are integers from 〇 to 4; 111 is 11 or 〇1_4 alkyl); And X is a group represented by formula (I c): This paper scale applies to Chinese National Standard (CNS) Α 4 specification (210 X 297 mm) 1 16334 (amendment) 1259188 H3 (Ic) Employees' Welfare Committee of the Central Bureau of the Ministry of Economic Affairs prints OH $ I -(O-CH2-CH-CH2O-M-) y [where y is an integer from 0 to 20; M is the basis of (I a), Or a group consisting of the formulas (El) and (E2): (E1) The formula shown by the following formula: (E1) -CO-, -CH2_, -C(CH3)2- or the following formula The base 圑-ch2-^Q)-ch2 or (E2) has the novolac epoxy resin ch2-ch-ch2 p-ch2-ch-ch2 -R1 -ch2- (E2) In the formula (E2), R1 is as defined above; d is an integer from 0 to 6; R2, R (independently, hydrazine or a group represented by the following formula; 16334 (amendment)) National Standard (CNS) A4 Specification (210X297 mm) I259l88 (where 'R1 is as defined above)]. 2 For example, the resin composition of the first application of the patent scope includes (1) an epoxy resin other than the phosphorus-containing epoxy resin represented by the formula U); (2) a hardener; (3) a hardening accelerator; 4) inorganic fillers; and (5) additives. 3 The resin composition of claim 2, wherein the component 〇) bis oxy-resin is an epoxy resin having two or more epoxy groups in one molecule. 4 » • 树脂 Resin composition of the scope of patent application No. 3, wherein: Ingredients:: The gas resin includes one or more selected from the group consisting of dihydroxybenzenes, bisphenols, difficult classification, various resins, aliphatic amines Aromatic amines, amine-based economics, Central Bureau of Standards, Bureau of Work and Welfare, printed carboxylic acid and compounds such as acid-lowering compounds, epoxidized reaction ring epoxy resin group. • The resin composition of item 4 of the 4th patent range, the towel, and the oxygen resin of the component (1) are glycidyl ether resins. 6. The resin composition of claim 5, wherein the glycidyl ether resin comprises - or a plurality selected from the group consisting of bismuth condensed glycidyl sulphate, bis bis hydrazine glycerin oxime, floc-core VIII p, knife one Know, glycerol ether, nitrogen ring-containing glycidyl 16334 (corrected paper " Zhang scale applicable medium specification (^^3*- 3 1259188 H3 2, And a group consisting of a resin composed of a phenolic polycondensate, a resin such as _, etc. 7. The resin composition of the second aspect of the patent application, wherein the component (7): the lipid hardener includes one or more It is selected from the group consisting of a compound containing an aryl group, a phosphorus compound, or a compound selected from the group consisting of / and not containing its own self. 8 · As claimed in the patent formula, the resin composition of the seventh item, the nitrogen content, the structure The compound has the structure represented by the following formula (Π): R4] (wherein R3 is a cva group, a phenyl group or a trapped r4; and a nitrogen atom or a group represented by (IIb), provided that at least one R4 is not a hydrogen atom: in the formula (Π a), η Is an integer of 2〇; R5 is a group represented by a phenylene group, an anthranyl group or a formula (Π a-Ι): printed by the Bureau of Economic Welfare of the Central Bureau of Standards (Ha-1) [In the formula (Ha-Ι), A is a chemical bond, -CH2·, -C(CH3)2- or a group of the following formula - S02_, -CO_ This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 public Chu) 4 16334 (amendment) 1259188 H3 -CH' Lu CH, or the above aromatic groups represented by R and A may be selected from one or more selected from a base group, a slow base, C! _ 6 :): Substituted substituents such as substituents; amines - (ch2-r5-ch2v (Hb) Printed by the Staff Standards Committee of the Central Bureau of Standards of the Ministry of Economic Affairs (lib), R5 and η are as defined above. 9 · The patent composition of the patent scope of the seventh resin composition, wherein the compound used as a hardening and does not contain _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ group. The resin composition according to any one of claims 7 to 9, wherein the hardener is added in an amount of 1 part by weight of the epoxy equivalent of the epoxy resin and the reactive hydrogen equivalent of the hardener. 〇: 5〇 to 1〇〇: 15〇. The resin composition of the first aspect of the invention, wherein the hardener is added in an amount of from 100:60 to 100 in terms of a ratio of an epoxy equivalent of the epoxy resin to a reactive hydrogen equivalent of the hardener: 140. 1 2 The resin composition of claim n, wherein the curing agent is added in an amount of 1 〇〇: 70 to 1 in terms of the ratio of the epoxy equivalent of the epoxy resin to the reactive hydrogen equivalent of the hardener. 〇〇: 1 3 〇. 13. The resin composition of claim 2, wherein the paper size of the component (3) is 1259188 H3 grade phosphine, quaternary ammonium hardening accelerator package - one or more selected from the group consisting of tertiary amines , salt, quaternary salt, -^ ^ ^ ^ boron difluoride complex, hydride, 1,8 diazepines (5,4, 〇) 十_ 石山μ 灭%-7-(DBU) A group consisting of an undecene compound and an imidazolide or a mixture thereof. The resin composition of the first aspect of the invention, wherein the modifier of the component (3) is selected from the group consisting of a tertiary amine, a tertiary phosphine, and an imidazole compound or a mixture thereof. 15. The resin composition as claimed in the patent application scope, wherein the hardening accelerator of the component (3) is selected from the group consisting of dimethylphenylamine, triphenylphosphine, 2-methyl-methyl rice, 2 - laughing A group consisting of glutinous rice, 2-ethyl-4-methylimidazole or a mixture thereof. 16 . The resin composition of claim 15 wherein the component (3) I? modifier is trisylphosphine, 2-mercaptoimid or a mixture thereof. The resin composition of any one of the first to third aspects of the invention, wherein the amount of the modifier is 〇·〇1 to 5% by weight based on the total weight of the epoxy resin composition. 18·If the material of the 17th item of the material range, the towel, the hardening of the Ministry of Economic Affairs, the Central Bureau of Standards, the Staff Welfare Committee printed, used in the total weight of 5 Hai epoxy resin composition of 0.05 to 3 weight%. 19. The resin composition wire filler according to claim 2, wherein the wire filler comprises - or a plurality selected from the group consisting of dioxygen powder, quartz, ^, talc, alumina powder, aluminum hydroxide powder, magnesium hydroxide powder, carbon A group consisting of a zinc-aluminum bismuth compound, a boron-nitrogen compound, or a mixture thereof. 16334 (Revised) This paper size coffee A4 specification - Gong Chu) 1259188 "Resin composition of the 19th patent dry circumference, in which the pain filling agent of the ingredient (4) is dioxotomy. 21 · If applying for a patent Fan 圚筮 π 阁 乐 20 resin composition, wherein the dioxide powder includes a spherical shape, prepared 22 ^ ^ in the use of $ 谷 二 二 结晶 结晶 结晶 结晶 结晶 。 = = = = = = The resin composition of item 19, wherein the inorganic filler d has an average particle size ranging from 1 to 40 " m, and the maximum particle size of the filler is also less than 150//m. For example, the scope of claims 19 to 22 The resin composition according to any one of the invention, wherein the addition ratio of the 2 ° blasting machine filler is 50 to 90% by weight based on the total weight of the epoxy resin composition. 2 4 · The resin composition of the second aspect of the patent application And the inorganic filler is added in an amount of from 5 5 to 87 % by weight based on the total weight of the epoxy resin composition. The resin composition according to claim 2, wherein the additive of the component (7) comprises Decane coupling agent, colorant, mold release agent and low stress additive The Employees' Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs prints the resin composition as claimed in Article 25 of the patent scope 'wherein the decane coupling agent includes vinyl trioxonane' vinyl triethoxy decane, n_(2_aminomethyl)- 3-aminopropyl-methyl-dioxanoxane, N_(2-aminoethyl)_3_aminopropyl-trioxoxane, 3-aminopropyl-triethoxyoxane, 3-phenylaminopropyl- Diethoxyoxane, 3-epoxypropylpropyl-trioxoxane, 3_epoxypropylpropyl-indenyl-dioxanoxane, 2_(3,4-epoxycyclohexyl)ethyl_ Trimethoxine, 3-methylpropoxypropyl-trimethoxysulfanyl, and 3-hydrothiopropyl-trioxoxalate:: End. 16334 (Revised) This paper scale applies to Chinese national standards. (CNS) A4 size (210X297 mm) 1259188 'Resin composition of Article 25 of the patent scope, wherein the colorant includes stone black and oxidizing agent. 28. Resin composition coloring material according to claim 27 For carbon black. 29. For the resin composition of the scope of claim 2 or 2, wherein the hardening time of the composition is controlled at 30 to 5 m mrc The viscosity is controlled in the range of 20 to 500 cps / 25 ° C. 30. The resin composition of the scope of the application of the second or the second is mainly used for semiconductor packaging, manufacturing of adhesive sheets, composite materials, laminated boards, printed circuits Substrate, copper foil adhesive used in the layering method. Printed by the Central Bureau of Standards and Staff Welfare Committee of the Ministry of Economic Affairs 16334 (Revised) This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 public Chu)