TWI228526B - Flame-retardant styrenic resin composition - Google Patents

Abstract

The present invention provides a flame-retardant styrenic resin composition, comprising: (A) a rubber-modified styrenic resin; (B) a bromic flame-retardant agent; (C) a antimony-containing oxide; wherein the content solvable in THF having a average molecular weight of from 2,000 to 50,000 within the component (A) is X wt.% based on the weight of total solvable contents, and the content having a average molecular weight of equal to or greater than 1,000,000 is Y wt.% based on the weight of total solvable contents; X/Y<1.5> <= 10.5, and X <= 25 wt%; and the content of bromine in the resin composition is equal to or greater than 8.5 wt.%, and the content of antimony in the resin composition is from 1.0 to 4.0 wt.%.

Description

1228526 Λ7 B7 V. Description of the invention (l) ~ The present invention relates to a styrene resin composition having excellent flame retardancy, especially a resin composition which can reduce the time of afterglow during combustion. Press' In the known technology, in order to make the styrene resin composition have flame retardant properties, it is generally added to the composition with flame retardants such as tooth, phosphorus or inorganic, and in order to achieve UL-94 V -0 flame retardancy requirements, the more the amount of flame retardant added, the better the composition's flame retardant effect; but the use of flame retardant in the evening will increase the proportion of the finished product. For downstream processing industry, resin The unit volume and cost will increase, and as far as the composition itself is concerned, a large amount of the flame retardant will also cause a reduction in impact strength and deterioration of physical properties such as thermal stability. In addition, the flame retardant is expensive. The use of multiple additions also increases costs during production. In addition, in a known technique, Japanese Patent Application Laid-Open No. 59_166552 describes that an i-based flame retardant is added to a styrene resin having a specific viscosity (7 / &gt; 0.4 dl / g), The composition of antimony trioxide (Sb203) and a small amount of ethylenebisstearylamine (EBA) can achieve the purpose of good flame resistance, but the resin composition has no effect on the afterflame residual phenomenon during combustion. 〇 The staff of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China printed the inventor to solve the above-mentioned shortcomings. After intensive research, he found that the molecular weight distribution of solubles in the styrene resin was controlled, and the content of halogens and antimony in the composition was controlled. , Can make the resin composition have excellent flame resistance, and reduce the residual time of afterflame during combustion. Therefore, the object of the present invention is to provide a flame retardant styrenic resin composition which has excellent flame retardancy and can reduce the residual time of afterflame during burning. _______ __ This paper is applicable to China National Standards (CNS) A4 size (210 '乂 297 mm) 1228526

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 0 The present invention is characterized in that the polystyrene resin composition comprises (A) a stupid vinyl resin modified by rubber; (B) a bromine flame retardant; (C) Antimony-containing oxides; among them, the soluble components in the component (A) which can be dissolved by tetrahydrofuran (butane HF) are distributed in the range of 2,000 to 50,000, which are all soluble X and Y satisfy the following relationship: x / Y15S10 · 5, XS25% by weight; meanwhile, the bromine content in the resin composition is greater than Or equal to 8.5 wt%, and the recorded content is 1.0 to 4.0 wt%: The above resin composition can not only prevent chattering, but also achieve UL_94 VQ level flame resistance, and its physical properties are also good. The rubber-modified styrene-based resin of the component (A) of the present invention refers to a graft copolymerized with a vinyl aromatic monomer and other copolymerizable monomers in the presence of a rubbery polymer. A branch copolymer, or a thermoplastic resin obtained by copolymerizing the above monomers and the above-mentioned graft copolymer, and / or poly a can be used in block polymerization, solution polymerization, or a combination of block solution and suspension, etc. the way. Vinyl aromatic monomers suitable for the present invention are: styrene, o-fluorenyl styrene, p-fluorenyl styrene, m-methylstyrene, 2, bis-fluorenyl styrene, ethyl styrene , Benzene of alkyl substitution type such as p-tert-butyl styrene, etc., and the scale scale is applicable to Zhongguanjia County (CNS) A4 Specification No. 4 I (210X 297 public poverty) ----- ^- --- * ': &gt; .- 士 ------ ^ ~~ *. · .¾, \ 呑 (Please read the notes on the back and fill in this page) 1228526 KB * Central Bureau of Standards, Ministry of Economic Affairs Printed by the Employees' Cooperative Cooperative 5. Description of the invention (4) X / Y15 $ 10.5, XS25% by weight, preferably X / Y15S10.0, XS23% by weight, more preferably X / Y15 $ 9.0, X $ 21% by weight; when 乂 is greater than 25 When the weight% or X /Y1·5>10.5, in the combustion test, afterglow flame is easy to form a residual flame (glowing) phenomenon; this phenomenon has been determined by the inventors of this case to study, the possible cause is the residual flame Residue is affected by the combination of lower molecular weight (X) and higher molecular weight (Y), that is, when there are too many low molecular weight parts or too few high molecular weight parts in component (A), the reduction cannot be achieved. The purpose of the afterflame residue phenomenon; in addition, the present invention restricts the content of the low molecular weight (X) to be less than 25% by weight because the overall viscosity is low when the content of the low molecular weight (X) is higher than 25% by weight. Increasing the proportion of high molecular weight (ie the part of Y) is not ideal for its modification effect. Therefore, only when the relationship of X /Y15S10.5 and XS25% by weight can be satisfied at the same time can the resin composition effectively prevent burning time. The occurrence of flame residue. The THF-soluble component of the component (A) of the present invention means that a rubber-modified styrene-based resin is dissolved in THF, and an insoluble substance (or a gel) insoluble in THF is filtered out by a filter. , That is, the soluble content of the component (A). The bromine-based flame retardants of the component (B) of the present invention are, for example, tetra bromo bis phenol A, tetra bromo bis A-bis (2-ethyl ether) [tetra bromo bis phenol A-bis -(2-hydroxy ethylether)], tetrabromobispan A-bis- (2,3-dimophenyl ether) [tetra bromo bis phenol A-bis_ (2,3-di bromo phenyl ether)], etc. Induced body A, etc .; or hexabromo di-phenyl ether, octabromo page 6 This paper applies Chinese National Standard (CNS) A4 (210X 297) (Please read the precautions on the back before filling this page),-?

1228526 A7 B7 V. Description of the invention (5) di-phenyl ether), decabromo diphenyl ether (deca bromd) (&quot; ΜΗ "'referred to as DE-83), bis (tribromophenoxy) ) Ethane [bis (td ^. Then

Phenoxy) ethane], hexabromocyclododecane, etc. or brominated epoxy resin flame retardants. The above-mentioned brominated epoxy resin flame retardant is obtained by reacting bromine-containing bisphenol A with chloro_1,2-epoxypropane. Among them, bromine-containing epoxy resin and bromine-containing bisphenol A are obtained. Reaction to obtain a high molecular weight brominated epoxy resin having an epoxy group or a phenol group at the end, which can also be used in the present invention. In addition, the present invention can also use a polyepoxy group brominated epoxy resin. Terminal phenyl etherified by reaction with phenol, alkylphenol, brominated phenol, dibromophenol, trichlorophenol, pentabromophenol, pentachlorophenol and the like. That is, the bromine-based flame retardant of the component (B) of the present invention can be represented by the following structural formula: (Please read the precautions on the back before filling in this page), etc.

CH3 OH R in the above structural formula represents a hydrogen atom or M. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -CH2-CH-CH2 ^ -CH2-CH-CH2-0-R5 »〇d) H and R ' Represents a lower alkyl group and / or a phenyl group substituted by a bromine atom, X represents an atom, i represents an integer of 1 to 4, and η is an integer of 0 to 30. In addition, other halogen compounds that can be used in the present invention are, for example, monobromophenol, tribromophenol, pentabromophenol, tribromo-cresol, dibromoisopropylphenol, tetrabromobisphenol S, and the like. In order to meet the flame-retardant requirements of UL-94 V-0, the paper on this page applies the Chinese National Standard (CNS) μ specification (210X297 mm line 1228526. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 V. Description of the invention (6)-The content of desert in 28.5 wt%, preferably the content of desert is 90 ~ 18% by weight, and the most preferable is 9.5 ~ 13% by weight; when the content of stream is less than 85% by weight , It is easy to cause a sudden increase in the number of seconds in the combustion test, and the mind method meets the requirements of a, v_〇 level. The recorded oxide of the component (C) of the present invention is a flame retardant, and its recorded content accounts for 1.0 of the resin composition. ~ 4.0% by weight, preferably 丨 · 5 ~ 3.7% by weight, more preferably 2.0 ~ 3.5% by weight, and specific antimony-containing oxides are, for example: antimony trioxide (SM) 3), five The main function of antimony oxide (also this) is to provide the auxiliary role of bromine compounds in suppressing the combustion mechanism. When the antimony content in the composition is insufficient, it cannot meet the requirements of UL-94 V_〇 level. The content of the component needs to be above a certain ratio to be clear. Effect, but when the antimony content is too high, for example: when it accounts for more than 40% by weight of the resin composition, the afterflame residue will increase, and its formation mechanism is not clear, but it is speculated that it may be due to the phenomenon of metal ion heat accumulation, making The agglomerated antimony-containing oxides form a heat concentration point, causing the afterflame phenomenon to continue. The flame retardant styrenic resin composition of the present invention may include other additives as needed. For example, in order to produce a black molded product, carbon black may be added to the resin. However, when carbon black is added to the composition, 0 重量 ％ 之间。 Residual Martian phenomenon of the resin composition is more obvious; the carbon black content (based on 100% by weight of the resin composition) added to the above black molded products, generally between 125 ~ 2.0% by weight. Other additives include: antioxidants, ultraviolet absorbers, lubricants, fillers, plasticizers, and antistatic agents. Among them, the antioxidants that can be used in the present invention are, for example, 2,6-di-tertiary butadiene (2-, 6-di-t-butyl-4-methyl phenol), trinonyl phenyl linolenic acid (tri _ page 8) This paper is in accordance with China National Standard (CNS) A4 (210X 297mm) (Please read the notes on the back before filling in this page}

1228526 Λ7 B7 1 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China 5. Description of the invention (7) nonyl phenyl phosphite), octadecyl_3_ (3,5_di-third-butyl-4-merylphenyl) ) Propionic acid S purpose [octadecyl-3- (3,5-di-t-butyl-4-hydroxy- 卩 1 ^ 1171) 卩 1: 〇 卩 1〇11 & {€], thio-diethylene -Bis (3,5-di-third-butyl-4-meryl- / 3-phenylpropionic acid) [thio diethylene bis (3,5-di-t-tert-4-hydroxy 117 (11 * 〇 ( ^ 1111 &amp; 11 ^ 6), tetrakis [methyl # group (3,5-di-third-butyl-4-meryl- / 5- „phenylpropionic acid)] methylbenzene {Tetrakis [methylene (3,5- di-t-tert-4-hydroxy hydrocirnamate)] methane}, 2,4-bis [(thiooctyl) methyl] -o-methyl {2,4-bis [(octyl thio) methyl] 0-cresol} , Tris (2,4-di-tert-butyl phenyl) phosphite [tris (2,4-di-tert-butyl phenyl) phosphite]}, Dilauryl thio di propionate), Di stearyl thio di propionate, triethylene glycol-bis-3- (3-third-butyl-4-hydroxy-5-methylphenyl) propane Ester [Tri ethylene glycol-bis-3- (3-1 &gt; butyl-4-hydroxy-5-methylphenyl) propionat e], 1,1-bis (2-methyl-4-hydroxy-5-third butylphenyl) butane [1, l-bis (2-methyl-4-hydroxy-5-t-butylphenyl) butane], etc. 0 and lubricants such as: calcium stearate, magnesium stearate, stearic acid _ zinc metal soap salts, ethylene bis stearyl amide (ethylene bis stearyl amide, referred to as EB A ), Ammonium distearate, ammonium palmitate, butyl stearate, palmityl stearate, polyglycerol monostearate, n-docosalic acid, stearic acid, etc. Polyethylene wax, montan wax, etc. When the resin composition of the present invention is manufactured, styrene resin, bromine flame retardant, thorium-containing oxide and other additives are added and kneaded together; The resin composition of the present invention is obtained, and the method of kneading is representative. Page 9 The paper size applies the Chinese National Standard (CNS) A4 (21 × 297 mm) gutter (please read the precautions on the back before filling in this Page) 1228526 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (8) It is generally used in many synthetic resin fields. Mix it with a Hanschel mixer, etc., and dry mix it with a mixer such as an extruder mixer, kneader, or Banbury mixer. In the above mixing method, when melting and kneading, or molding using the molding method described later, if the resin composition of the present invention is subjected to a high temperature action, it will cause thermal decomposition or dehydrohalogenation reaction, so the mixing temperature should be controlled to 180 ~ 250 ° C; When molding using the resin composition of the present invention, molding methods such as injection molding, extrusion molding, compression molding, and hollow molding are generally applicable. Physical property test I. Determination of average molecular weight and molecular weight distribution: determined according to the following conditions of gel dialysis method (GPC): column: KD-806M detector: RI-410, UV-486 mobile phase: tetrahydrofuran (Referred to as THF), the flow rate of l.Oc.c./min. That is, in the measurement range of GPC, the total integrated area of resin signals with a molecular weight of 2,000 to 12,000,000 is taken as 100%, and the integrated area of resin between 2,000 and 50,000 accounts for X% of the total area, and the total area of 1,000,000 or more accounts for the total Y% of area. 2. Izod Impact Strength (IZ): According to ASTM D-256 (with notch, thickness is 1/8 inch), the unit is kg-cm / cm. 3. Tensile strength (Tsy): tested in accordance with ASTM D-638, the unit is kg / cm2 〇 page 10 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the back (Please fill in this page again)

1T 1228526 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Λ7 B7 V. Description of the invention (9) IV. Combustion test: According to the UL-94 V-0 test standard, the flame-retardant styrene resin composition of the present invention is taken The plastic sheet (125mm X 13mm X 2.5mm) has been tested for its burning time after flame burning; it passes the test as "0" and fails as "X". V. Afterglow test (glowing test): The afterflame Mars burns during the combustion test; that is, the number of seconds that the residual Mars continues to burn until the flame is completely extinguished after the flame test on the test piece is extinguished during the plastic test. [Preparation Example] [Preparation Example 1] The rubber-modified styrene resin (A-1) feed composition includes: 86% by weight of a styrene monomer, 7% by weight of ethylbenzene, and 6.675% by weight of polybutadiene. Ene rubber (low cis-butadiene rubber with Mooney viscosity of 35 cps, molecular weight of 450,000, and vinyl structure of 12% by weight), 0.3% by weight of 2,6-di-tert-butyl-4-methylphenol, And 0.025% by weight of the starter, and then the above feed composition was pumped into three plug flow reactors each with a volume of 110 liters at a flow rate of 50 liters b per hour, and the reaction temperature gradually increased from 105 ° C To 175 ° C, and a product with a final conversion of 72% by weight was obtained. After the foregoing product was removed from the solvent, a rubber-modified styrene resin (A-1) was obtained. [Preparation Example 2] The rubber-modified styrene resin (A-2) contained 85.7% by weight of styrene monomer, 7% by weight of ethylbenzene, 7.05% by weight of polybutadiene rubber, and 0.25% by weight. % Octadecyl-3- (3,5-di-tert-butyl-4-merylphenyl) propionate is added with 0.015% by weight of the starter, of which _ page 11 Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) --------- Approved clothing ------ II ------ ^ (Please read the precautions on the back before (Fill in this page) 1228526 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. After the description of the invention (10), the above feed composition is also pumped into the three plug flows with a volume of 110 liters at a flow rate of 50 liters per hour In the reaction tank, the reaction temperature is gradually increased from 105 to 190 ° C, and the final conversion rate of 81% by weight is obtained. After removing the solvent, styrene modified by rubber can be obtained. Resin (A-2). [Preparation Example 3] The rubber-modified styrene resin (A-3) was prepared under the same conditions as in Preparation Example 2, but the styrene monomer in the feed composition was changed to 84.7% by weight, and 1.0% by weight was added. High molecular weight (molecular weight 1,700,000) polystyrene can be used to prepare rubber-modified styrene ethyl resin (A-3) 〇 [Preparation Example 4] rubber-modified styrene resin (A-4) In the same manner as in Preparation Example 2, the styrene monomer in the feed composition of f was changed to 84.7% by weight, and high molecular weight (molecular weight 1,700,000) polystyrene was added at ΐ · 0% by weight, and the third The temperature of the reaction tank is raised to 205 ° C, and a rubber-modified styrene resin (A-4) having a final conversion rate of about 90% can be obtained. [Preparation Example 5] rubber-modified benzene Ethylene resin (A · 5) has the same composition and reaction conditions as in Preparation Example 2, but the styrene monomer in the feed composition is changed to 80.7% by weight, and 5.0% by weight of a medium molecular weight (molecular weight 420,000) polystyrene is added, that is, A rubber-modified styrene resin (A-5) can be obtained. [Preparation Example 6] A rubber-modified styrene resin (A-6) is composed of a feed: 85.4 4% by weight of styrene monomer. / 〇 ethylbenzene, 7.5 wt% polybutadiene rubber (high cis rubber, Taipol-015H of Taiwan Rubber Company), 0.05 wt% octadecyl-3- (3,5 · di- Tertiary butyl _ page 12 ___ This paper size applies to Chinese National Standard (CNS) A4 size (iiox 297 mm) &quot; &quot; &quot; (Please read the precautions on the back before filling this page) — Order 1228526 A7 B7 4, Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (η-4-Cerylphenyl) propionate, 3.02 weight ° / 〇 stone butterfly oil, and 0.03% by weight of the start [Production Example 7] The rubber modified styrene resin (A-7) has the same composition and reaction conditions as in Production Example 2, but the amount of the starting agent in the feed composition is reduced to 0.015% by weight, and The amount of styrene monomer used was 85.415% by weight, the temperature of the third reaction tank was raised to 185 ° C, and the final conversion rate was about 85%. [Example] [Example 1] Take 78.5% by weight of styrene resin (A)), 17.0% by weight of brominated epoxy resin (hereinafter referred to as EC-14, which is bromine manufactured by Dainippon INK &amp; Chemical Inc. The amount is 58.5%, molecular weight ι, 400% of flame retardant), 3.5% by weight of antimony trioxide, and 10% by weight of carbon black. The aforementioned ingredients are evenly mixed in an extruder. After mixing, Extruded from a perforated plate into a rubber strip, cooled in a water bath, dried and pelletized, and then formed an UL combustion test piece and a physical property test piece of 1/1 忖 through an injection machine, and performed various physical properties and combustion tests. The results are shown in Table 1. [Example 2] The manufacturing method of Example 1 was the same, except that the styrene resin was changed to [made by (A-6) in the preparation example. The measured test pieces also had various physical properties and combustion. The test and measurement results are also shown in Table 1. [Example 3] Same as the manufacturing method of Example 1, except that 79% by weight of styrene tree was used. Order ------ line (please read the notes on the back before filling in this page) ^ The paper size is applicable to the Chinese National Standard (CNS) f Printed by Zhongyin Zhuanjigong Co., Ltd. I228526 S_ 一 __ 一 五2. Description of the invention (I2) grease (Α-3), and the use amount of antimony trioxide is changed to 3.0% by weight. The measured test pieces also undergo various physical properties and combustion. The test results are also shown in Table 1. [Example 4] Same manufacturing method as in Example 1, but the feed composition was changed to: ^ wt% styrene resin (A-1), 10.8wt% decabromo Diphenyl ether (Deca bromo di phenyl ether, which is a flame retardant, hereinafter referred to as DE-83), 4.1 Zhongli A's "One Record" and ΐ · 〇 reset% of nasty black, the same test strips Various physical properties and combustion tests were carried out. The measured results are also shown in Table 1. [Example 5] The feed composition of Example 4 was the same, but the styrene resin (A-1) was changed to 82.0% by weight, DE-83 was increased to 14.0% by weight, and antimony trioxide was changed to 3% by weight / The test piece prepared by ′ was also subjected to various physical properties and combustion tests. The measured results are also shown in Table 1. [Example 6] The feed composition of Example 4 was the same, except that the styrene resin was changed to 83.0% by weight, DE-83 was changed to 14.0% by weight, and antimony trioxide was changed to 30% by weight. For carbon black, the test pieces prepared were also subjected to various physical properties and combustion tests. The measured results are also shown in Table 1. [Comparative Example] [Comparative Example 1] The same method as in Example 1 was used, but the type of styrene resin in the feed composition was changed from (A-1) to (A-2). Item Properties _____i_14 ¥ This paper size is applicable to Chinese National Standard (CNS) A4 specifications (Please read the precautions on the back first to complete this page) 4 丨 Order 1228526 Α: Β ~ 4- ΦΤ Μ. Employees ’consumption by the Central Bureau of Standards Printed by the cooperative V. Description of the invention (I3 and combustion test, the measured results are also shown in Table 1. [Comparative Example 2] Same as the manufacturing method of Example 1, except that the styrene resin in the feed composition was (A-1) It was changed to (A-7), and the obtained test piece was also subjected to various physical properties and combustion tests, and the measurement results are also shown in Table 1. [Comparative Example 3] Same as the manufacturing method of Example 1, but in the feed composition The styrene resin was changed from (A-1) to 79.0% by weight (A-4), and the amount of antimony trioxide was reduced to 3.0% by weight. The test pieces obtained were also subjected to various physical properties and combustion tests. The measurement results are also shown in Table 1. [Comparative Example 4] Same as the manufacturing method of Example 1, but the styrene resin (A -1) It was reduced to 77.0% by weight, and the amount of antimony trioxide used was increased to 5.0% by weight. The test pieces prepared were also subjected to various physical properties and combustion tests. The results are also shown in Table 1. [ Comparative Example 5] Same as the manufacturing method of Example 1, but the feed composition was changed to: 74.9% by weight of acetophenone resin (A-6), 20.0% by weight of EC-14, and 4.1% by weight of trioxide. Antimony and 1.0% by weight of carbon black, the test pieces prepared were also subjected to various physical properties and combustion tests, and the measurement results are also shown in Table 1. [Comparative Example 6] Same as the manufacturing method of Example 4, but The styrene resin (A-1) in the feed composition was reduced to 82.7% by weight, and the use amount of antimony trioxide was increased to 5.5% by weight. The test pieces prepared were also subjected to various physical properties and combustion tests. Test ---- page 15 This paper is suitable for the family and the family ^ 7〇 Milk) A4 size (210X 297 Gongchu) —--------- --------- 士 Κ ---- --Ding_ ϋ m ___ US. 、 -Mouth (please read the precautions on the back before filling this page) 口 28526 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (Η) The results are also shown in the table One[Comparative Example 7] The manufacturing method of Example 4 was the same, but the styrene resin in the feed composition was changed to 82.0% by weight (A-2), and the usage amount of _83 was increased to 14.0% by weight. The amount used was reduced to 3.0% by weight. The test pieces prepared were also subjected to various physical properties and combustion tests. The measurement results are also shown in Table 1. [Comparative Example 8] The manufacturing method of Example 4 was the same, but the feed composition was changed to: π ′% by weight of styrene resin (A-4), 16.0% by weight of DE-83, and 38% by weight of dioxide. Records, and 1.0% by weight of farming, households 刽 厌 ^… I feel annoyed… the test piece of the same I also carried out various physical properties and combustion tests, the measurement results are also shown in Table-. [Comparative Example 9] The same manufacturing method as in Example 4 except that the feed composition was changed to: by weight% stupid vinyl resin (A-5), 14.0% by weight DE-83, 3.0% by weight = dioxide Records, and 1.0% by weight of charcoal, the so-called qi qi ^…… the test piece of the same I also carried out various physical properties and combustion tests, the measurement results are also shown in Table _. [Comparative Example 10] The same manufacturing method as in Example 4 was used, but the feed composition was changed to: 802% by weight of styrene resin (A-4), 16.0% by weight of de-83, α1 s tongue M, and Dong The test specimens prepared were also subjected to various physical properties and combustion tests. The test results are also shown in Table 1. [Comparative Example 11] The same production method as in Example 1 was used, but the feed composition was changed to: 83.5 wt%. Styrene resin (A-1), 12.0% by weight of flame retardant EC_14 (bromine content 7 I ----- I-; .--. • clothing — I (Please read the precautions on the back before filling in this Page), -port 4 0 page 16 This paper size applies Chinese National Standard (CNS) A4 specification (21 × X 297 mm) 1228526 A7 V. Description of the invention (15) 'Weight i / 〇) 3.5 Weight 1 / 〇 No. 2 dioxide, and 10 weight. For carbon black, the test piece produced by the test results showed that its flame retardancy is insufficient, and there is a dripping phenomenon. At the same time, it cannot pass the UL-94 ν-〇 combustion test standard. It is known from the foregoing examples-six that the present invention controls the proportional relationship between the low molecular weight (χ) and the higher molecular weight (=) of the THF soluble content of the vinyl-modified resin ⑷ modified by rubber, and cooperates to control the composition The bromine content and antimony content in the substance can not only maintain the good physical properties of the resin, but also pass the I #flame test of UL_94 乂 _0, and reduce the time for the residual flame to remain when the composition is burned. The test results of 5, 5 and 7 show that when the value of χ / γ1 · 5 is greater than 10.5, the composition fails to pass the UL-94 V-0 flame retardant grade and the residual time is high. According to Comparative Examples 3 and 8, , 9, 10 Experimental results = When the value of (X) is less than 25% by weight, the resin composition also fails the flame resistance test, and the residual time of afterflame is high when burning; and the experimental results of Comparative Examples 4, 6 It is known that when the content of antimony in the resin composition is higher than 4% by weight, the expected effect of the present invention cannot be achieved. ^ However, the above are only a few of the preferred and feasible embodiments of the present invention. For those skilled in the art, modifications or changes made in accordance with the spirit and scope of the present invention should be included in the scope of patent application for this case. --- ------ Batch clothes ------, 玎 ------ ^ (Please read the notes on the back before filling this page) M. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

1228526

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I This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm)

Claims (1)

1228 ^ 24n ^ sL / ^ myc with! _______D8_ Six 'scope of patent application (revision of patent application scope of invention No. 88123318) (93 〇6) 1. A kind of flame-resistant stupid vinyl resin composition, the composition contains: (A) rubber modified benzene Ethylene resins are resins made from vinyl aromatic monomers as main components and grafted with other copolymerizable monomers in the presence of rubbery polymers; (B) brominated flame retardants; It is selected from tetrabromobisphenol A inducers such as tetrabromobisphenol A, tetrabromobisphenol A_bis (2-hydroxyethyl ether), tetrabromobisphenol ^ bis_ (2,3-dibromophenyl ether), etc .; Hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromocyclododecylbenzene, etc. or brominated epoxy resin flame retardants (C) Bromide-containing oxide, which is selected from the group consisting of: antimony trioxide and antimony pentoxide; wherein the molecular weight distribution of soluble components in the component (A) that can be dissolved by tetrahydrofuran (THF) is 2,0. 〇〇〜5〇 ， 〇〇〇 accounts for X% of all solubles, and molecular weight greater than or equal to ^ 00,000 accounts for Y% of all solubles, the above X, Y meet the following requirements Formula:% X 10 · 5,25 by weight; the same resin composition bromine content greater than or equal to 8.5 wt 0 / square, and the content of antimony in 1 billion · · 〇~4 wt%. 2. According to the flame-retardant styrene ethyl resin resin composition described in item 1 of the scope of patent application, wherein X / Υ1_5 $ 10.0 · 23% by weight. 3. According to the flame-retardant styrene-ethylated resin composition according to item 1 of the scope of the patent application, the content of antimony is 1.5 to 3.5% by weight. 4. According to the national standard of flame-retardant styrene-based resins described in item 1 of the scope of the patent application, the national standard of the paper (CNf from specifications (21Gx 297)) ^-Page 18 1228526 ABCD \ F τ- · / b year patent application composition, in which the rubbery polymer is a diene rubber, which is selected from the group consisting of: butadiene rubber, polystyrene-butadiene copolymer, polyisoprene rubber, polyethylene -Propylene-diene rubber. This paper size applies to China National Standard (CNS) A4 (210x 297 mm) page 19