TW200838883A - Flameproof copolymer and flame retardant thermoplastic resin composition including the same - Google Patents

Abstract

Disclosed herein is a flameproof copolymer comprising repeating units of (A) about 80-99% by weight of a (meth)acrylic monomer and (B) about 1-20% by weight of a vinyl-containing phosphorous monomer. The present invention also provides a thermoplastic resin having good flame retardancy by using the flameproof copolymer.

Description

200838883 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fireproof copolymer and a flame retardant thermoplastic resin composition comprising the same. More particularly, the present invention relates to a fire-resistant copolymer comprising a vinyl-containing phosphorus monomer having a specific structure and an acrylic monomer, and a flame-retardant thermoplastic resin comprising the same.

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20 [Prior Art] Generally, a'-propionic acid early-form resin has good transparency, financial property, mechanical properties, and excellent thermal stability. Therefore, acrylic monomer sapphire has been widely used in electronic products, display members, optical materials, building members, and automotive components, and is also applied to common molds. Acrylic resins, in particular, have good scratch resistance and are therefore increasingly used in the external components of electrical appliances or electrical products. However, the acrylic resin is basically a flammable substance, resulting in a limited application range of the acrylic resin. V is proposed to add a w 芏哗 芏哗 I , , , , , , , , , , , , , , , , , , , , , , , , , , 7 1 The soil and the mouth are fried with ",,", and, in order to achieve the preset flame retardancy, a large amount of flame retardant must still be used, _ ^ ^ ", and this method is also due to flame retardancy. It is dissolved and has an external fat, and it has problems such as a core, an acrylic-based tree, a L-, a property, and a deterioration in mechanical properties. Therefore, it has been proposed to add a scale to the polymer chain to solve these problems. (4) The invention is based on the disclosure of a non-saturated monomer, bis(hydrocarbyl)vinyl phosphonate, and acrylic acid or a flame retardant copolymer disclosed in US Pat. No. 4,035,571. Methacrylic acid is copolymerized. 5 However, this method faces the problem that a large amount of bis(hydrocarbyl)vinylphosphonate must be used in order to obtain sufficient flame retardancy, which causes poor mechanical properties and also imposes application limitations. therefore, The inventors of the present invention have developed a fire-retardant copolymer and a package containing a flame-retardant thermoplastic resin composition having a specific structure of a vinyl group-containing phosphorus monomer (phosphorus content of 18 to 30% by weight) Copolymerized with methacrylic acid monomer, in addition to maintaining mechanical properties, it also has the same good fire resistance, transparency, and scratch resistance. [Invention] 15 The main purpose of this paper is to provide a flame retardant. A thermoplastic resin composition. Another object of the present invention is to provide a thermoplastic resin composition having good transparency and scratch resistance while having good flame retardancy. A further object of the present invention is to provide a pair Eco-environment-free heat 2〇 plastic resin composition, when it burns, does not produce toxic gases such as dioxin " fusphon or hydrogen halide gas. A further object of the present invention is to provide a good coordination of physical properties. Thermoplastic Resin Compositions 200838883 Other objects and advantages of the present invention will become apparent from the disclosure and claims. An embodiment of the present invention provides a fire-resistant copolymer comprising repeating unit (a) from about 80 to 99 weight percent of a (meth)acrylic monomer; and (b) about 1 Up to 20% by weight of a vinyl-containing phosphorous monomer. In an exemplary embodiment of the invention, the vinyl-containing phosphorus monomer may comprise from about 18 to 30 weight percent phosphorus. A method of performing sadness is a method for the manufacture of a fire-resistant copolymer. The method comprises: copolymerizing a monomethacrylic monomer at a temperature of about 60 to 90 ° C in the presence of a radical initiator. And a vinyl-containing phosphorous monomer for 1 to 6 hours. Further, the present invention provides a flame-retardant thermoplastic resin composition comprising the above fire-resistant copolymer. The resin composition was measured by a Nippon Denshoku haze meter after measuring a sample having a thickness of 3 mm, and the haze of the resin composition was 2% or less; after the measurement by JIS K 5401, the pencil hardness of the resin composition was about 2H; after a 1/8" thick test sample is measured by ASTM D-256, the Izod impact strength of the resin composition is about 〇kgf.cm/cm or more; After the test sample was measured by ASTM D-1525, the heat resistance (VST) of the resin composition 20 was about 97 ° C or more; and the flame retardancy of the resin composition after the test sample of 2.0 mm thick was tested by UL 94. It is ν·2, V-1 or V-0. The resin composition of the present invention may further comprise an additive selected from the group consisting of an impact modifier, an anti-dripping agent, a phenol resin, and a flame retardant. Agent (flame 7 200838883 retardant), flame retardant aid, lubricant, antioxidant, plasticizer, thermal stabilizer, light stabilizer A group consisting of a stabilizer, a pigment, a dye, an inorganic filler, and a mixture thereof. In an exemplary embodiment of the present invention, the impact modifier may be used in an amount of about 30 parts by weight or less based on 100 parts by weight of the fire-resistant copolymer. The rubber modified graft copolymer can be used as an impact modifier. In an exemplary embodiment of the present invention, the anti-dripping agent may be used in an amount of about 2 parts by weight or less based on 10 100 parts by weight of the fire-resistant copolymer. In one embodiment, the phenol resin may be used in an amount of from 1 to 20 parts by weight based on 100 parts by weight of the fire-resistant copolymer. In another embodiment, after the resin composition is measured by a Nippon Denshoku haze meter with a test sample of 3 mm thick, the haze of the resin composition can be about 17% or less; after being measured by JIS K 5401, the resin The pencil hardness of the composition is about 2H; after a 1/8" thick test sample is measured by ASTM D-256, the resin composition has an Izod impact strength of about L3 kgf.cm/cm or more; "The thickness of the test sample is measured by ASTM D-1525. The heat resistance (VST) of the resin composition is about 95 ° C or more; and the resistance of the resin composition after the test of the sample of 2.0 mm thick by UL 94 is tested. The flammability is V-2, V-1 or V-0. Further, the present invention provides a mold of this resin composition. The fire-retardant copolymer of the present invention comprises a repeating unit (a) a mercaptoacrylic monomer and (b) a vinyl-containing phosphorous monomer. 8 200838883 Examples of the methacrylic acid monomer (a) may include, but are not limited to, an acrylate, an alkyl acrylate, a methacrylate, or a methacrylic acid ( Alkyl (meth)acrylate), or methacrylic acid. These can be used alone or in combination with each other. Preferably, the methyl propyl enoic acid monomer is methacrylate, methyl (meth) acrylate, ethyl (meth) acrylate , propyl (meth)acrylate, butyl (meth)acrylate, pentyl(meth)acrylate, cyclohexyl methacrylate (cyclohexyl methacrylate) Cyclohexyl(meth)acrylate), n.hexyl(meth)acrylate ^glyCidyl(meth)acrylate,methic acid (meth) . The vinyl group-containing monomer (b) may be selected from one or more of the compounds as shown in the chemical formula.

[Chemical Formula 1] [Chemical Formula 2]

20 dropout 3]

[Chemical Formula 4]

9 200838883 (In the above Chemical Formulas 1 to 4, I is hydrogen or a methyl group, R2 and R3 are independently a mercapto group or an ethyl group, and η is 0 or 1). 5

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20 Examples of the compound represented by Chemical Formula 1 may be dimethylvinylphosphineoxide, ethylmethylvinylphosphineoxide, diethylvinylphosphineoxide, dimethyl 2 fluorenyl Dimethyl phosphine oxide (dimethyl 2-methylvinyl|>hosphineoxide), ethylmethyl 2-methylvinylphosphineoxide, diethyl 2-methylethylene phosphine oxide (diethyl) 2_methylvinylphosphineoxide), dimethylvinylphosphinate, ethylmethylvinylphosphiiiate, diethylvinylphosphinate, dimethyl 2-methyl Dimethyl 2-methylvinylphosphinate, ethylmethyl 2-methylvinylphosphinate, diethyl 2-methylvinylphosphinic acid Diethyl 2-methylvinylphosphinate), dimethylvinylphosphoiiate, ethyl hydrazine Vinylphosphonate-diethylvinylphosphonate, dimethyl 2-methylvinylphosphonate, ethyl fluorenyl 2-methylethylene Ethylphosphonate (ethylmethyl 2-methylvinylphosphonate) or diethyl 2- 2-methylvinylphosphonate (diethyl 25 2-methylvinylphosphonate). 200838883

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20 Examples of the compound represented by Chemical Formula 2 may be allyldimethylphosphixieoxide, allylmethylethylphosphineoxide, allyldiethylphosphineoxide, 2-methyl 2-methylallyldimethylphosphineoxide, 2-methylallylmethylethylphosphineoxide, 2-methylallyldiethylphosphineoxide ), allyldimethylphosphinate, allylmethylethylphosphinate, allyldiethylphosphinate, 2-mercapto 2-metliylanyldimethylphosphinate, 2-methylallylmethylethylphosphinate, 2-methylallyl diethyl phosphinate (2-methylallyldimethylethylphosphinate) 2-methylallyldiethylphosphinate), allyldimethylphosphonate, allylmethylethylphosphonic acid S (allylmethylethy) Lphosphonate), allyldiethylphosphonate, 2-methylallyldimethylphosplionate, 2-methylpropylpropylmethylphosphonate (2-methylallylmethylethylphosphonate), or 2-methylallyldiethylphosphonate. Examples of the compound of the formula 3 may be vinyldimethylphosphinate or vinyl. Ethylmethylphosphinate, vinyl hydrazide diethylphosphinate, 11 200838883 5

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(vinyldiethylphosphiiiate), 2-methylvinyldimethylphosphinate, 2-methylvinylmethylethylphosphinate, 2-mercaptovinyl acrylate 2-methylvinyldiethylphospliinate, vinyldimethylphosphonate, vinylethylmethylphosphonate, vinyldiethylphosphonate, 2-methylvinyldimethylphosphonate, 2-methylvinylethylmetliylphosphonate, 2·mercaptoethyldiethylphosphine 2-methylvinyldiethylphosphonate, dimethylvinylphosphate, ethylmethylvinylphosphate, diethylvinylphosphate, dimethyl 2- Dimethyl 2-methylvinylphosphate, ethylmethyl 2-methylvinylpethyl Hosphate), or diethyl 2-methylvinylphosphate. Examples of the compound represented by Chemical Formula 4 may be allyldimethylphosphinate, allylethylphosphinate 20, and allyl diethylphosphinic acid vinegar (allylethylmethylphosphinate). Allyldiethylphosphinate), 2-methylallyldimethylphosphinate, 2-methylallylmethylethylphosphinate, 2-mercaptopropyl 2-methylallyldiethylphosphinate, 12 200838883 allyldimethylphosphoiiate, allylethylmethylphosphonate, allyldiethylphosphine Acidyl (allyldiethylphosphoiiate), 2-methylallyldimethylphosphiosphonate, 2-methylallylethylmethylphosphonate, 2-methyl 2-methylallyldiethylpliosphonate, allyldimethylphosphate, allyldimethylmethyl sulphate Allylethylmethylphosphate), allyldiethylphosphate, 2-methylallyldimethylphosphate, 2-methylallylethylmethyl citrate (2-methylallylethylmetliylphosphate), or 2-methylallyldiethylphosphate. The structure of the vinyl group-containing phosphorus monomer (b) preferably contains about 18 to 30 15 weight percent of phosphorus, and more preferably about 20 to 29 weight percent of phosphorus. If the phosphorus content used in the vinyl phosphorus compound is less than about 18% by weight, the copolymer does not have sufficient flame retardancy. Further, if the content of the filler used in the vinyl phosphorus compound is more than 30% by weight, the compatibility may be lowered. In one embodiment of the invention, the copolymer may comprise from about 80 to 90 weight percent of the mercaptoacrylic acid monomer and from about 5 to about 20 weight percent of the repeating unit of the vinyl-containing phosphorous monomer. When the amount of the vinyl group-containing phosphorus monomer used is in the above range, high flame retardancy and good mechanical properties can be obtained. More preferably, it is a fluorenyl acrylate monomer having about 85 to 95 weight percent and a vinyl group-containing phosphorus monomer having a weight percentage of about 5 to 15 13 200838883. A preferred example of the ethyl group-containing phosphorus monomer (C) may be dimethylvinylphosphonate (DM VP). A method of preparing a vinyl-containing phosphorous monomer (C) is disclosed in Japanese Patent No. 3,836,459, the entire disclosure of which is incorporated herein by reference. The fire-retardant copolymer of the present invention can be produced by a general copolymerization reaction in which a vinyl group-containing phosphorus monomer is added to a methacrylic acid monomer in the presence of a radical initiator. Since the vinyl group-containing phosphorus monomer has a polymerizable vinyl group, the vinyl group-containing phosphorus monomer and the methacrylic monomer can form a main chain together. When copolymerizing, it is optional to add an unsaturated group containing a monomer such as an aromatic vinyl monomer. The content of the methacrylic monomer and the vinyl group-containing phosphorus monomer can be controlled by adding an unsaturated group containing a monomer before the repeating unit of the final copolymer can reach the above ratio. In one embodiment of the present invention, a mercaptoacrylic acid monomer and a vinyl group-containing phosphorus monomer may be added to a reactor, followed by copolymerization at a temperature of about 60 to 90 ° C in the presence of an initiator. 1-6 hours. Suitable starters can be, but are not limited to, such as benzoyl peroxide (ΒΡΌ), dicumyl peroxide (20 DCP), di-tert-butyl peroxide (di) -tert-butylperoxide, DTBP), azobisisobutyronitrile (AIBN), and similar free radical initiators. The fire-resistant copolymer of the present invention can be used in a general acrylic resin. For example, the fire-resistant copolymer may be used alone or as a thermoplastic resin composition in combination with other resins or additives, to improve impact strength and flame retardancy. ',,, impact-resistant modifier 5 The flame-retardant thermoplastic resin composition of the present invention may further contain an anti-impact modifier as needed. The impact modifier can be prepared by grafting a resin polymer with a vinyl monomer. The damage of the impact modifier can be graft copolymerized onto a rubber polymer by combining an aromatic vinyl monomer and a selectively copolymerizable monomer. 10 This rubber can be selected from diene-based rubbers such as polybutadiene rubber and poly(styrene-butadiene) rubber. And poly(acrylonitrile-butadiene) rubber; saturated rubber added with hydrogen to diene rubber; isoprene rubber; acrylic rubber; At least one rubber polymer in a group consisting of a silicon rubber, an ethylene/propylene rubber, and an ethylene-propylene-diene terpolymer (EPDM) Things. Among these rubbers, a diene-based rubber is preferred, and a butadiene-based rubber is more preferred. The rubber content is preferably 20 parts by weight of from about 5 to about 65 parts by weight based on 100% by weight of the graft copolymer resin. The rubber copolymer preferably has an average particle diameter of about 0.1 to 4 μm in consideration of the impact strength and appearance of the mold. The impact modifier may be used in an amount of about 30 parts by weight or less based on 100 parts by weight of the fire-resistant copolymer, preferably from about 0.1 to 20 parts by weight, and more preferably from about 0.5 to 15 parts by weight. If the amount of the impact modifier 25 is more than 30 parts by weight, the flame retardancy may be lowered. 15 200838883 Anti-drip agent The flame-retardant thermoplastic resin composition of the present invention may further contain a primary anti-dripping agent as needed. The anti-dripping agent may be an additive which is present in the resin in a fibrous form after being mixed with the resin. Examples of the anti-dripping agent may be a resin which is mainly agglomerated, such as polytetrafluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropylene, tetrafluoroethylene and perfluorooctene. Perfluoroalkylvinylether fluorinated 10 carbon resin and polyvinylidide dieflioriride anti-drip agent are preferably used in an amount of about 100 parts by weight of the fire-retardant copolymer. 2 parts by weight or less. When the anti-dripping agent is used in an amount exceeding 2 parts by weight, the impact strength may be deteriorated. Among the fluorine-based resins, polytetrafluoroethylene is preferred. 15 Phenolic Resin The resin composition of the present invention may further comprise a phenol > resin as a coke forming agent. Since the phenol resin can form a coke at a low temperature (about 300 to 450 ° C), coke can be efficiently formed on the surface at the initial stage of combustion. 20 Phenolic resins are generally classified into resol-type phenol resins and novolak-type resins. In the present invention, the thermoplastic resin is more preferable than the thermosetting resin. The thermoplastic resin may include a phenol formaldehyde thermoplastic resin, a tertiary butylphenol formaldehyde thermoplastic resin, a para octylphenol formaldehyde thermoplastic resin, and a cyanogen. Para 16 200838883 cyanophenol formaldehyde thermoplastic resin, phenolepoxy thermoplastic resin, and mixtures thereof. The thermoplastic phenol resin preferably has an average molecular weight (Mw) of from about 300 to about 1 Torr. The phenol resin may comprise from about 1 to 5 to about 20 parts by weight, and preferably from about 1 to about 1 part by weight, per 100 parts by weight of the fire-resistant copolymer. If the content of the phenol resin is more than about 20 parts by weight, deterioration of mechanical properties and poor weather resistance are caused. The resin composition of the present invention may further comprise an additive selected from the group consisting of a flame retardant, a flame retardant aid, a lubricant, an antioxidant, an plasticizer, and a plasticizer. A group consisting of a plasticizer, a thermal stabilizer, a iight stabilizer, an inorganic filler, a pigmented one, a 11^1^, and a dye. These additives may be used singly or in combination with each other. The flame retardant may be a phosphorus flame retardant or a halogen flame retardant, and is preferably a phosphorus 15 flame retardant. Examples of the phosphorus flame retardant may include red phosphorus, phosphate, phosphonate, phosphinate, phosphine oxide, and nitrogen-filled compound. (phosphazene), its metal salts, and their analogs. Among them, the most preferred is an aromatic acid-filled phosphate compound. The flame retardant is preferably used in an amount of about 30 parts by weight or less, and more preferably about 0.1 to 15 parts by weight, per 100 parts by weight of the fire-retardant copolymer, and most preferably It is from 0.3 to 10 parts by weight. If the content of the flame retardant is more than 30 parts by weight, mechanical properties such as flame retardancy and impact strength may be deteriorated. 17 200838883 4 The resin composition of the present invention can be produced by a general process method. For example, all ingredients and additives can be mixed together and then extruded through an extruder to produce pellets. Further, the resin composition of the present invention can be used in various mold products 5. In particular, the resin composition is suitable for use in electronic or electrical products such as home televisions, computers, audio sets, air conditioners, automated office equipment, and the like. The invention is further described with reference to the following examples, which are intended to be illustrative only and not to limit the scope of the invention, and the scope of the invention is defined by the scope of the invention. EXAMPLES Example 1 90 parts by weight of decyl decyl acrylate, 10 parts by weight of dimethylethene 15 alkenylphosphonate (containing 22.76 weight percent of phosphorus), and 0.3 parts by weight of benzoquinone peroxide Rhodium was added to a reactor and reacted at 80 ° C for 3 hours. The resulting polymer was dried in a vacuum oven to obtain a flame retardant PMMA copolymer (VP-PMMA). Next, this VP-PMMA copolymer was passed through a twin screw extruder and extruded into pellets at 200 to 260 °C. Using a 8 oz shot 20 out molding machine, the pellets were made into test dies at 25 (TC and cylinder temperature 60 ° C. Example 2 18 200838883 • Example 2 Implementation Method and Example 1 was the same except that 5 parts by weight of EXL-2602 (methyl methacrylate-butadiene-acrylic acid copolymer) (manufactured by MRC Co.) was added as an impact modifier. Example 3 Example 3 The method was the same as in Example 2 except that 0.5 part by weight of polytetrafluoroethylene (Teflon 30J manufactured by Mitsui-Dupont Co., Ltd.) was further added as an anti-dripping agent. 10 Example 4 Embodiment Method and Example of Example 4 1 is the same except that 0.5 part by weight of polytetrafluoroethylene (Teflon 30J manufactured by Mitsui-Dupont Co., Ltd.) is added as a primary anti-dripping agent. 15 Comparative Example 1 The method of the first embodiment is the same as that of the embodiment 1, except 75 parts by weight of a conventional PMMA copolymer containing no dimethylvinylphosphonate (L-84 manufactured by LG Chern Co., Korea) was used in place of the flame-retardant PMMA copolymer of the present invention, and added between 25 parts by weight. Hydroquinone bis(2,6-dimethylphenylphosphonate) (resorcinol bis (2) 6dimethylphenylphosphate), ΡΧ-20Ό manufactured by Daihac M Chemical Co.) as a flame retardant. Comparative Example 2 200838883 'Comparative method of Comparative Example 2 is the same as Comparative Example 1 except that 5 parts by weight of EXL-2602 is further added ( Methyl methacrylate-butadiene-acrylic acid copolymer (manufactured by MRC Co.) was used as an anti-impact modifier. Comparative Example 3 The comparison method of Comparative Example 3 was the same as that of Comparative Example 2 except that yttrium was further added. 5 parts by weight of polytetrafluoroethylene (Teflon 30J manufactured by Mitsui-Dupont Co., Ltd.) was used as a primary anti-dripping agent. 10 Comparative Example 4 The comparison method of Comparative Example 4 was the same as that of Comparative Example 1, except that 0·5 was further added. The polytetraethylene ethylene (Teflon 30J manufactured by Mitsui-Dupont Co., Ltd.) was used as a primary anti-dripping agent. 15 The physical properties of the test molds produced in the comparative examples and the examples were tested by the following methods, and the test results are shown in the following table. (1) Haze (%): The measurement of haze (%) is based on a 3 mm thick test sample measured by a Nippon Denshoku haze meter. 20 (2) Wrong hardness: 23 JIS K 5401 is used after 48 hours of exposure at °C and relative humidity of 50%. The pencil hardness of the mold of l〇xl〇cm2. The scratch resistance is measured by 3B, B, HB, F, H, 2H, 3H, etc. The higher the resistance is, the higher the resistance is, the higher the B is the resistance. The worse the scratching property. (3) Ehrlich impact strength: Notched Ep ι and R impact strength is measured using 25 ASTM D-256 (l/8 inch, kgf-cm/cm) 〇20 200838883 (4) Heat resistance (VST): domain softening temperature (Vicat Softening

The measurement of Temperature was measured using ASTM D-1525 (l/4n inch, kgf.cm/cm) at a load of 5 kgf (°C). (5) Flame retardancy: Measurement of flame retardancy, measured by UL 94 with a test sample of 2.0 mm thick. [Table 1] Example Comparative Example 1 2 3 4 1 2 3 4 Content (parts by weight) VP-PMMA 100 100 100 100 - - - One PMMA - - - - 75 75 75 75 Impact modifier - 5 5 - - 5 5 PX-200 - - - - 25 25 25 25 PTFE - 0.5 0.5 - - 0.5 0.5 Physical properties Haze 1.5 15.5 16.8 3.9 6.9 33.3 35.7 8.2 Pencil hardness 3H 2H 2H 3H 2H Η Η 2Η Ehrliar impact strength 1.4 4.5 4.7 1.6 1.1 3.3 3.8 1.3 VST (°C) 97.3 96.5 96.9 97.1 78.2 77.5 78.9 78.1 UL94 V2 V2 VI V0 V2 Failure ignition fire * Failure: UL flame retardant grade is not available, * Fire: Test molds are burnt. 10 As shown in Table 1, Example 1 had good transparency, staggered hardness, and heat retention due to low haze. Example 2 has a low but sufficient transparency because it contains an anti-impact modifier, and has good uniform physical properties such as impact strength and flame retardancy. The use of PTFE as an anti-dripping agent 15 Examples 3 to 4 showed slight changes in physical properties, and compared with Examples 1 to 2, the fire resistance of Examples 3 to 4 was improved to VI and V0. On the contrary, using Comparative Examples 1 to 4 of the conventional PMMA, even if it has the same amount of phosphorus as in Examples 1 to 4, the comparison 21 200838883 Examples 1 to 4 still have poor flame retardancy and poor flame resistance. Flame resistance. And its flame resistance is also greatly reduced. The present invention has been described in detail with reference to the preferred embodiments of the present invention. The scope and scope shall be based on the definition of the scope of patent application. [Simple description of the diagram] None 10 [Description of main component symbols] None 22

Claims (1)

200838883 X. Patent application scope: 1. A fire-resistant copolymer comprising repeating units: (A) 80 to 99% by weight of methacrylic (meth)acrylic monomer; and 5 (B) 1 to 20 by weight Percent of vinyl-containing phosphorous monomers. 2. The fire-resistant copolymer according to claim 1, wherein the vinyl-containing phosphorus monomer (B) is selected from at least one of the compounds represented by Chemical Formulas 1 to 4 [4匕2] 10 [Chemical Formula 1] Ψ' % Η匕学式3] [Chemical Formula 4] 15 (wherein I is hydrogen or methyl, R 2 and R 3 are independently methyl or ethyl, and η is 0 or 1) 〇 3. The fire-retardant copolymer of claim 1 wherein the The vinyl phosphorus monomer (Β) contains 18 to 30% by weight of phosphorus. 4. The fire-retardant copolymer according to claim 1, wherein the methacrylic monomer (Α) is selected from the group consisting of methacrylate (meth)acrylate and methacrylate (metliyl). Meth)acrylate), 23 200838883 ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, A Pentyl(meth)acrylate, cyclohexyl(meth)acrylate, n-hexyl(meth)acrylate,methacrylic acid ring A group consisting of glycidyl (meth) acrylate, (methic acid), and mixtures thereof. A flame-retardant thermoplastic resin composition comprising the fire-retardant copolymer according to any one of items 1 to 4 of the application. 6. The flame-retardant thermoplastic resin composition according to claim 5, wherein the resin composition has a haze of 2 after a 3 mm thick test sample is measured by a Nippon Denshoku haze meter. % or less; after the measurement by JIS K 5401, the pencil hardness of the resin composition is 2H; 15 Izod impact of the resin composition after being measured by ASTM D-256 as a 1/8" thick test sample The strength is 1.3 kgf.cm/cm or more; after the 1/4" thick test sample is measured by ASTM D-1525, the heat resistance (VST) of the resin composition is 97 ° C or more, and The flame retardancy of the resin composition was V-2, V-1 or V-0 after being tested by UL 94 for a 2.0 mm thick test sample. 20 7 - A mold which is produced by using a flame-retardant thermoplastic resin composition as described in claim 5 of the patent application. 8. The flame-retardant thermoplastic resin composition of claim 5, further comprising at least one additive selected from the group consisting of an impact modifier and an anti-drip agent (anti- Dripping agent), hope 24 200838883 phenol resin, flame retardant, flame retardant aid, lubricant, antioxidant, plasticizer , a thermal stabilizer, a light stabilizer, a pignieiit, a dye, an inorganic filler (〖11〇1§31^!11161:) and a mixture thereof Group. 9. The flame-retardant thermoplastic resin composition according to claim 8, wherein the impact modifier is used in an amount of 30 parts by weight or less based on 100 parts by weight of the fluorene-based copolymer. The flame-retardant thermoplastic resin composition as described in claim 8 wherein the anti-dripping agent is used in an amount of 2 parts by weight or less based on 100 parts by weight of the fire-resistant copolymer. 11. The flame-retardant thermoplastic resin composition according to claim 8, wherein the phenol resin is used in an amount of 1 to 20 parts by weight or less based on 100 parts by weight of the fire-resistant copolymer. 12. The flame-retardant thermoplastic resin composition as described in claim 8 wherein the resin composition has a haze of a resin composition of a test thickness of 3 mm thick by Nippon Denshoku 17% or less 'UIS K 5401 After Summer' The hardness of the resin composition is 2h; 20 After the test sample of 1/8" thickness is measured by ASTM D-256, the resin composition has an Ehrlich impact The strength is 1.3 kgf.cm/cm or more; after the 1/4" thick test sample is measured by ASTM D-1525, the resin composition has a heat resistance (VST) of 95 ° C or more; and is 2.0 mm thick. After the test sample was tested by UL 94, the flame retardancy of the resin composition was V-2, V-1 or V-0. 25 200838883, ^ 13. A mold made of a flame-retardant thermoplastic resin composition as described in claim 8 of the patent application. A method for preparing a fire-resistant copolymer, comprising: a monomethicone monomer 5 and a vinyl group-containing phosphorus monomer at 60 to 90 ° C in the presence of a radical initiator Copolymerization is carried out for 1 to 6 hours. 26 200838883 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: