KR20110076705A - Flameproof acrylic copolymer and method of preparing the same - Google Patents

Abstract

PURPOSE: A flameproof acrylic copolymer is provided to ensure excellent fire retardant characteristic and impact resistance even if additional flame retardant and impact modifier are used and not to prevent toxic gases such as hydrogen halide gas. CONSTITUTION: A copolymer resin is such that a polyurethane oligomer is grafted in a polymer including (A) 60-90 weight% of a (meth)acrylic monomer and (B) 10-40 weight% of a vinyl group-containing phosphorous-based monomer. The polyurethane oligomer is grafted in the amount of 1-10 parts by weight based on 100 parts by weight of a polymer including the (meth)acrylic monomer and the vinyl group-containing phosphorous-based monomer. The average molecular weight of the copolymer resin is 50,000-500,000 g/mol.

Description

Acrylic flame retardant copolymer and its manufacturing method {Flameproof Acrylic Copolymer and Method of Preparing the Same}

The present invention relates to an acrylic flame retardant copolymer and a method for producing the same. More specifically, the present invention relates to a flame retardant copolymer prepared by grafting a polyurethane oligomer to a copolymer of a (meth) acrylic monomer and a vinyl group-containing phosphorus monomer, and a method for producing the same.

In general, acrylic resins are excellent in transparency, weather resistance, light weight, non-toxicity, colorability and mechanical properties, and are widely used in food container materials, materials of electrical and electronic products, optical materials, automotive materials, and building materials. In particular, acrylic resins have excellent scratch resistance, and are being applied as coating materials, optical materials, and exterior materials for electrical and electronic products. The demand is expected to increase significantly in the future. However, acrylic resins have a weak impact strength and are flammable, and their use is limited.

In order to increase the flame retardancy of such acrylic resin, a method of injecting a low-molecular weight impact modifier and a flame retardant into the acrylic resin has been proposed. However, in order to obtain the desired impact resistance and flame retardant properties, a large amount of additives are required, which causes a disadvantage in that excellent transparency, appearance, heat resistance, and mechanical properties, which are inherent properties of the acrylic resin, are reduced.

On the other hand, in order to solve the disadvantages caused by the addition of additives, a method of introducing a halogen or phosphorus flame retardant to the polymer chain has been proposed. In addition, a method of copolymerizing and blending an acrylic monomer with butadiene, butyl acrylate and the like has been proposed to improve the impact strength of the acrylic resin.

For example, US Pat. No. 4,035,571 discloses flame retardant copolymers copolymerizing unsaturated monomers, bis (hydrocarbyl) vinyl phosphonates and acrylic or methacrylic acid. However, in the above method, a large amount of bis hydrocarbyl) vinyl phosphonate should be added in order to secure sufficient flame retardancy, and thus there is a disadvantage in that the use thereof is extremely limited due to deterioration of heat resistance, mechanical properties, and the like of acrylic resin.

U. S. Patent No. 6,319, 966 discloses a method of forming a polymer such as butyl acrylate, butadiene, styrene and grafting to an acrylic resin to improve the impact strength of the acrylic resin. However, this method also does not significantly improve the impact strength and does not improve the problem of flame retardancy.

An object of the present invention is to provide a copolymer not only excellent in flame retardancy but also excellent in impact strength.

Another object of the present invention is to provide a copolymer that exhibits excellent flame retardancy and impact strength even when not used in combination with an additional flame retardant and impact modifier.

Another object of the present invention is to provide an environmentally friendly flame retardant copolymer that does not generate toxic gases such as hydrogen halide gas during processing or combustion.

Another object of the present invention is to provide a method for preparing the grafted copolymer.

Another object of the present invention is to provide a thermoplastic resin composition comprising the copolymer.

The above and other objects of the present invention can be achieved by the present invention described in detail below.

In order to achieve the above technical problem, the present invention provides a polymer (C) polyurethane oligomer is grafted to a polymer comprising (A) 60 to 90% by weight of the (meth) acrylic monomer and 10 to 40% by weight of the (B) vinyl group-containing phosphorus monomer It provides a copolymer resin characterized in that.

In one embodiment of the present invention, the polyurethane oligomer (C) is 1 to 10 parts by weight based on 100 parts by weight of a polymer comprising the (meth) acrylic monomer (A) and the vinyl group-containing phosphorus monomer (B) It may have been.

In another embodiment of the present invention, the weight average molecular weight of the copolymer, characterized in that the polyurethane oligomer is grafted may be 50,000 to 500,000 g / mol.

In another embodiment of the present invention, the (meth) acrylic monomer (A)

(Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hydroxy ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, At least one monomer selected from the group consisting of cyclohexyl (meth) acrylate, n-hexyl (meth) acrylate, glycidyl (meth) acrylate and (meth) acrylic acid; And a (meth) acrylic monomer having a hydroxyl group.

In another embodiment of the present invention, the vinyl group-containing phosphorus monomer (B) is selected from the group consisting of compounds represented by the following formulas (1) to (4) and mixtures thereof.

[Formula 1] [Formula 2]

[Formula 3] [Formula 4]

In Formulas 1 to 4, R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are each independently a methyl group or an ethyl group, n is 0 or 1.

In another embodiment of the present invention, the vinyl group-containing phosphorus monomer (B) is dimethyl vinylphosphonate or dimethyl allylphosphonate.

In another embodiment of the present invention, the phosphorus content of the vinyl group-containing phosphorus monomer (B) is 15 to 30% by weight.

In another embodiment of the present invention, the polyurethane oligomer (C) may be prepared by polymerizing diisocyanate and diol.

In another embodiment of the invention, the diisocyanate is at least one selected from the group consisting of diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and butylene diisocyanate.

In another embodiment of the present invention, the diol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and polycarbonate diol.

In another embodiment of the present invention, the equivalent ratio of diisocyanate and diol is 1.0 to 3.0.

In order to achieve the above another technical problem, the present invention is to polymerize a monomer mixture comprising 60 to 90% by weight of (A) (meth) acrylic monomer and 10 to 40% by weight of (B) vinyl group-containing phosphorus monomer to form a polymer. step; And it provides a method for producing a copolymer resin comprising the step of grafting the (C) polyurethane oligomer to the polymer formed.

In order to achieve the above another technical problem, the present invention provides a molded article manufactured using the copolymer resin.

In Chemical Formulas 1 to 4, R ₁ is hydrogen, the present invention has excellent flame resistance and impact strength as well as excellent scratch resistance, etc., without further mixing other impact modifiers and flame retardants.

Hereinafter, the present invention will be described in more detail.

Acrylic Flame Retardant Copolymer

(C) Polyurethane oligomer is grafted to the polymer containing (A) 60-90 weight% of (meth) acrylic monomers and 10-40 weight% of (B) vinyl-group containing phosphorus monomers Provide resin.

The weight average molecular weight of the copolymer characterized in that the polyurethane oligomer is grafted is characterized in that 50,000 to 500,000 g / mol.

(A) (meth) acrylic monomer

In a specific example, as the (meth) acrylic monomer, (meth) acrylate, alkyl (meth) acrylate, hydroxy alkyl (meth) acrylate, (meth) acrylic acid, or the like can be used.

Specifically, (meth) acrylate, methyl (meth) acrylate, hydroxy ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) At least one monomer selected from the group consisting of acrylate, cyclohexyl (meth) acrylate, n-hexyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid; And (meth) acrylic monomers having a hydroxy group can be mixed and used, but is not necessarily limited thereto.

Here, (meth) acrylate means either or both of methacrylate and acrylate.

The (meth) acrylic monomer having the hydroxy group is mixed for the purpose of providing a reactor for grafting the (C) polyurethane oligomer.

(B) vinyl group-containing phosphorus monomer

It is preferable that the said vinyl group containing phosphorus monomer is contained in the ratio of 10-40 weight% with respect to 60-90 weight% of (A) (meth) acrylic-type monomer. When the content of the vinyl group-containing phosphorus monomer is less than 10% by weight, it is difficult to obtain a sufficient flame retardant effect, and when it exceeds 40% by weight, the mechanical properties of the copolymer may be lowered, which is not preferable.

In one embodiment, the vinyl group-containing phosphorus monomer may be selected from the group consisting of compounds represented by the following formulas (1) to (4) and mixtures thereof.

[Formula 1] [Formula 2]

[Formula 3] [Formula 4]

In Formulas 1 to 4, R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are each independently a methyl group or an ethyl group, n is 0 or 1.

In another embodiment, the compound represented by Formula 1 is vinyl dimethyl phosphine oxide, vinyl methyl ethyl phosphine oxide, vinyl diethyl phosphine oxide, 1-methylvinyl dimethyl phosphine oxide, 1-methylvinyl methyl ethyl phosphine Oxide, 1-methylvinyl diethyl phosphine oxide, methyl vinyl (methyl) phosphinate, methyl vinyl (ethyl) phosphinate, ethyl vinyl (methyl) phosphinate, ethyl vinyl (ethyl) phosphinate, methyl 1 -Methylvinyl (methyl) phosphinate, methyl 1-methylvinyl (ethyl) phosphinate, ethyl 1-methylvinyl (methyl) phosphinate, ethyl 1-methylvinyl (ethyl) phosphinate, dimethyl vinylphospho Acetate, methyl ethyl vinylphosphonate, diethyl vinylphosphonate, dimethyl 1-methylvinylphosphonate, methyl ethyl 1-methylvinylphosphonate, diethyl 1-methylvinylphosphonate, and the like.

In another embodiment, the compound represented by Formula 2 is allyl dimethyl phosphine oxide, allyl methyl ethyl phosphine oxide, allyl diethyl phosphine oxide, 2-methylallyl dimethyl phosphine oxide, 2-methylallyl methyl ethyl phosph Pinoxide, 2-methylallyl diethyl phosphine oxide, methyl allyl (methyl) phosphinate, methyl allyl (ethyl) phosphineate, ethyl allyl (methyl) phosphinate, ethyl allyl (ethyl) phosphinate, methyl 2-methylallyl (methyl) phosphinate, methyl 2-methylallyl (ethyl) phosphinate, ethyl 2-methylallyl (methyl) phosphinate, ethyl 2-methylallyl (ethyl) phosphinate, dimethyl allylphosph Phosphate, methyl ethyl allylphosphonate, diethyl allylphosphonate, dimethyl 2-methylallylphosphonate, methyl ethyl 2-methylallylphosphonate, diethyl 2-methylallylphosphonate, and the like.

In another embodiment, the compound represented by Chemical Formula 3 is vinyl dimethylphosphinate, vinyl ethyl (methyl) phosphinate, vinyl diethylphosphinate, 1-methylvinyl dimethylphosphinate, 1-methylvinyl ethyl (Methyl) phosphinate, 1-methylvinyl diethylphosphinate, vinyl methyl methylphosphonate, vinyl ethyl methylphosphonate, vinyl methyl ethylphosphonate, vinyl ethyl ethylphosphonate, 1-methylvinyl methyl Methylphosphonate, 1-methylvinyl ethyl methylphosphonate, 1-methylvinyl methyl ethylphosphonate, 1-methylvinyl ethyl ethylphosphonate, dimethyl vinyl phosphate, ethyl methyl vinyl phosphate, diethyl vinyl phosphate, dimethyl 1-methylvinyl phosphate, ethyl methyl 1-methylvinyl phosphate, diethyl 1-methylvinyl phosphate, and the like.

In another embodiment, the compound represented by Formula 4 is allyl dimethylphosphinate, allyl ethyl (methyl) phosphinate, allyl diethylphosphinate, 2-methylallyl dimethylphosphinate, 2-methylallyl ethyl (Methyl) phosphinate, 2-methylallyl diethylphosphinate, allyl methyl methylphosphonate, allyl ethyl methylphosphonate, allyl methyl ethyl phosphonate, allyl ethyl ethylphosphonate, 2-methylallyl methyl Methylphosphonate, 2-methylallyl ethyl methylphosphonate, 2-methylallyl methyl ethyl phosphonate, 2-methylallyl ethyl ethylphosphonate, allyl dimethyl phosphate, allyl ethyl methyl phosphate, allyl diethyl phosphate, 2 -Methylallyl dimethyl phosphate, 2-methylallyl ethyl methyl phosphate, 2-methylallyl diethyl phosphate, and the like.

In another embodiment, the vinyl group-containing phosphorus monomer is preferably dimethyl vinylphosphonate (DMVP) or dimethyl allylphosphonate (DMAP).

A method for producing the vinyl group-containing phosphorus monomer (C) is disclosed in Japanese Patent No. 3836459, which includes the present invention by reference.

In an embodiment, the vinyl group-containing phosphorus monomer used in the present invention preferably contains 10 to 30% by weight of phosphorus in the structural formula. If a vinyl-based phosphorus compound having a phosphorus content of less than 10% by weight is applied, it is difficult to secure sufficient flame retardancy. In addition, vinyl-based phosphorus compounds having a phosphorus content of more than 30% by weight are difficult to prepare, and the reactivity in the copolymerization reaction is poor.

(C) polyurethane oligomer

The polyurethane oligomer (C) is characterized in that 1 to 10 parts by weight is grafted to 100 parts by weight of the polymer polymerized monomer mixture including (A) and (B).

When the content of the grafted polyurethane oligomer (C) exceeds 10 parts by weight, the copolymer may have a decrease in heat resistance and pencil hardness, and also may cause a decrease in transparency, which is not preferable.

In one embodiment, the grafted polyurethane oligomer can be polymerized by selecting (B) as a material consisting of an organic polyisocyanate and a polymeric polyol. In another embodiment, the grafted polyurethane oligomer is (B) an organic di Isocyanates and polymer diols may be selected and polymerized. Organic diisocyanates include diphenyl methane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, and the like. Polymeric diols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, Polycarbonate diols and the like.

In another embodiment, the polyurethane oligomer of the present invention has an equivalent ratio of organic diisocyanate and polymer diol, that is, a molar ratio of terminal isocyanate molar ratio and terminal polymer diol of 1.0 to 3.0, preferably 1.0 to 2.0. As the molar ratio of the terminal isocyanate mole ratio and the terminal polymer diol is close to 1, the molecular weight of the oligomer increases.

Method for producing acrylic flame retardant copolymer

The present invention also comprises the steps of polymerizing a monomer mixture comprising (A) 60 to 90% by weight of (meth) acrylic monomers and 10 to 40% by weight of (B) vinyl group-containing phosphorus monomers to form a polymer; And it provides a method for producing a copolymer resin comprising the step of grafting (C) polyurethane oligomer to the formed polymer.

In one embodiment of the present invention, the flame retardant copolymer (A) is a (meth) acrylic monomer vinyl group-containing phosphorus monomer to the reactor and in the presence of an initiator at 60 to 180 ℃, preferably 80 to 140 ℃ 1 It may be prepared by polymerization for from 8 hours, preferably 2 to 6 hours.

 In another embodiment, the polyurethane oligomer (C) may be grafted 1 to 10 parts by weight based on 100 parts by weight of the polymer formed by polymerizing the monomer mixture including the (A) and (B).

In another embodiment, the polyurethane oligomer (C) is polymerized, including diisocyanates and diols. The polyurethane oligomer (C) is reacted with an organic isocyanate and a polymer diol, while stirring for 60 to 240 minutes, preferably 80 to 120 minutes at 60 to 100 ℃, preferably 70 to 90 ℃ in a nitrogen stream It can manufacture.

In another embodiment, the equivalent ratio of diisocyanate and diol is 1.0 to 3.0, preferably 1.0 to 2.0.

Resin composition containing acrylic flame retardant copolymer

The present invention also provides a thermoplastic resin composition comprising the grafted copolymer resin. The grafted flame retardant copolymer may be used in the form of a composition mixed with various additives to achieve better performance.

The additives that can be used include flame retardant aids, lubricants, anti drip agents, antioxidants, plasticizers, heat stabilizers, light stabilizers, pigments, dyes, inorganic additives, and the like, but are not necessarily limited thereto. The additives may be applied alone or in mixture of two or more. The additive is preferably used in an amount of 30 parts by weight or less, more preferably 0.001 to 30 parts by weight, based on 100 parts by weight of the grafted copolymer.

The composition comprising the grafted flame retardant copolymer can be prepared by a general method. For example, the grafted flame-retardant copolymer and other additives may be mixed at the same time, and then melt-extruded in an extruder to produce pellets or in the form of sheets, films, fibers, and the like.

Molded articles made of acrylic flame retardant copolymer

The invention also provides a molded article produced using the grafted flame retardant copolymer according to the invention. The grafted flame retardant copolymer according to the present invention not only has excellent flame retardancy and impact strength, but also has excellent scratch resistance and the like. Therefore, the polyurethane-grafted flame-retardant copolymer can mold products that exhibit excellent performance without mixing with other impact modifiers and flame retardants. For example, the grafted flame retardant copolymers, by themselves, are suitable for the production of electrical and electronic products such as TVs, computers, audio, air conditioners and office automation equipment, food containers, optical products and automotive articles.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

79 parts by weight of methyl methacrylate (MMA), 1 part by weight of 2-hydroxy methacrylate (2-HEMA), 20 parts by weight of dimethyl arylphosphonate (DMAP), 1,1-bis (tert) as an initiator 0.1 parts by weight of -butyl peroxy) cyclohexane was added, followed by stirring at 120 ° C. for 4 hours to prepare a flame retardant copolymer. Preparation of the polyurethane oligomer was carried out by reacting 1.2 equivalents of diphenylmethane-4,4'-diisocyanate and 1 equivalent of polyethylene glycol (molecular weight 1500) in a reactor while stirring for 90 minutes at 80 DEG C in a nitrogen gas stream. Polyurethane oligomer having isocyanate at the sock end was prepared. Each of the polymers prepared as described above was added 95 parts by weight of the flame retardant copolymer and 5 parts by weight of the polyurethane oligomer to the reactor and stirred for 120 minutes at 120 ° C. in a nitrogen gas stream to prepare a polyurethane-grafted flame retardant copolymer. The prepared grafted flame retardant copolymers were analyzed using 1H-NMR and FT-IR, and it was confirmed that the isocyanate disappeared and the urethane bond group was grafted through the newly formed.

The resulting copolymer was dried in a vacuum oven to obtain a grafted flame retardant copolymer, and then extruded in a conventional twin screw extruder at a temperature range of 200 to 260 ° C. to prepare pellets. The prepared pellets were dried at 80 ° C. for 3 hours, and then injected into an 8 Oz injection machine under conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare specimens.

Example 2

97 parts by weight of each of the flame retardant copolymers prepared as described above and 3 parts by weight of the polyurethane oligomer were added thereto, followed by stirring for 120 minutes at 120 ° C. in a nitrogen gas stream to prepare a polyurethane-grafted flame retardant copolymer. The resulting polymer was dried in a vacuum oven to produce a grafted flame retardant copolymer. The prepared grafted flame-retardant copolymer was processed in the same manner as in Example 1 to prepare a specimen.

Example 3

92 parts by weight of the flame retardant copolymers prepared in Example 1 and 8 parts by weight of the polyurethane oligomer were added thereto, followed by stirring for 120 minutes at 120 ° C. in a nitrogen gas stream to prepare a polyurethane-grafted flame retardant copolymer. The resulting polymer was dried in a vacuum oven to produce a grafted flame retardant copolymer. The prepared grafted flame-retardant copolymer was processed in the same manner as in Example 1 to prepare a specimen.

 Example 4

78 parts by weight of methyl methacrylate (MMA), 2 parts by weight of 2-hydroxy methacrylate (2-HEMA), 20 parts by weight of dimethyl arylphosphonate (DMAP), and 1,1-bis as an initiator 0.1 part by weight of (tert-butylperoxy) cyclohexane was added and stirred at 120 ° C. for 4 hours to prepare a flame retardant copolymer. The preparation of the polyurethane oligomer was carried out by reacting 1.5 equivalents of diphenylmethane-4,4'-diisocyanate and 1 equivalent of polyethylene glycol (molecular weight 1500) in a reactor while stirring for 90 minutes at 80 캜 in a nitrogen gas stream. Polyurethane oligomer having isocyanate at the sock end was prepared. After preparing the polymers as described above, 95 parts by weight of the flame retardant copolymer and 5 parts by weight of the polyurethane oligomer were added to the reactor, and the mixture was stirred at 120 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane-grafted flame retardant copolymer. The resulting grafted flame retardant copolymer was processed in the same manner as in Example 1 to prepare a specimen.

Comparative Example 1

80 parts by weight of methyl methacrylate (MMA), 20 parts by weight of dimethyl arylphosphonate (DMAP), and 1,1-bis (tert-butylperoxy) cyclohexane 0.1 as an initiator without adding a polyurethane oligomer. After the addition of parts by weight, the reaction was stirred at 120 ° C. for 4 hours. The resulting polymer was dried in a vacuum oven to produce a grafted flame retardant copolymer. The prepared grafted flame-retardant copolymer was processed in the same manner as in Example 1 to prepare a specimen.

Comparative Example 2

78 parts by weight of methyl methacrylate (MMA), 2 parts by weight of 2-hydroxy methacrylate (2-HEMA), 20 parts by weight of dimethyl arylphosphonate (DMAP), and 1,1-bis (initiator) 0.1 part by weight of tert-butylperoxy) cyclohexane was added and stirred at 120 ° C. for 4 hours to prepare a flame retardant copolymer. The preparation of the polyurethane oligomer was carried out by reacting 1.5 equivalents of diphenylmethane-4,4'-diisocyanate and 1 equivalent of polyethylene glycol (molecular weight 1500) in a reactor while stirring for 90 minutes at 80 캜 in a nitrogen gas stream. Polyurethane oligomer having isocyanate was prepared at the sock end. After preparing the polymers as described above, 80 parts by weight of the flame retardant copolymer and 20 parts by weight of the polyurethane oligomer were added to the reactor and stirred for 120 minutes at 120 ° C. in a nitrogen gas stream. A flame retardant copolymer grafted with polyurethane was prepared. The resulting graft copolymer was dissolved in dimethylformamide and precipitated in methanol to remove unreacted monomer and then recovered. The prepared grafted flame retardant copolymer was processed in the same manner as in Example 1 to prepare a specimen.

Comparative Example 3

79 parts by weight of methyl methacrylate (MMA), 1 part by weight of 2-hydroxy methacrylate (2-HEMA), 20 parts by weight of dimethyl arylphosphonate (DMAP), and 1,1-bis (initiator) 0.1 part by weight of tert-butylperoxy) cyclohexane was added and stirred at 120 ° C. for 4 hours to prepare a flame retardant copolymer. 95 parts by weight of the flame-retardant material prepared as described above and 5 parts by weight of MRC's EXL-2602 (Methyl methacrylate-Butadiene-Acrylate copolymer) as an impact modifier were extruded in a conventional twin screw extruder at a temperature range of 200 ~ 260 ℃ pellets Prepared as phase. The prepared pellets were dried at 80 ° C. for 3 hours, and then injected into an 8 Oz injection machine under conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare specimens.

Physical properties of the specimens prepared according to the Examples and Comparative Examples were evaluated according to the following methods, and the measurement results are shown in Table 1.

(1) Pencil hardness: After leaving the specimen 10 × 10 ㎠ for 48 hours at 23 ℃, 50% relative humidity, the pencil hardness was measured according to JIS K 5401 standard. Scratch resistance is evaluated as 3B, 2B, B, HB, F, H, 2H, 3H, etc. according to the result of pencil hardness.The higher the H value, the better the scratch resistance and the higher the B value, the lower the scratch property. do.

(2) Izod impact strength was measured according to ASTM D-256 standard at 1/8 "thickness (kgfcm / cm).

(3) Heat resistance (VST): measured at a load of 5 Kg in accordance with ASTM D-1525 standard at 1/4 "thickness.

(4) Flame retardant: Flame retardant was measured according to UL 94 flame retardant at 2.0 mm thickness.

 * Examples 4 and 1 have different molar ratios of terminal isocyanates and polymer diols (in Example 1, the capping ratio is 1.2, which means that the ratio of diol is relatively higher than that of Example 4 having a capping ratio of 1.5). If the ratio of diol is high, the impact strength tends to be better).

 ** Grafted Polyurethane Weight Ratio

As shown in Table 1, the grafted flame retardant copolymers Examples 1 to 4 prepared according to the present invention had excellent flame retardancy of the V1 to V2 grade, it was confirmed that the impact strength is also excellent. Moreover, it turned out that Examples 1-4 are excellent in heat resistance at 95 degreeC or more, and have the outstanding pencil hardness of H grade or more. In addition, the polyurethane-grafted flame retardant copolymer was found to have a high impact strength.

On the other hand, Comparative Example 1 was shown to have a low impact strength but excellent flame retardancy and pencil hardness. And in the flame retardant copolymer in which 12 parts by weight of polyurethane oligomer is grafted as in Comparative Example 2, the impact strength was high, but it was found that heat resistance and pencil hardness were lowered. In addition, in Comparative Example 3 prepared by mixing a flame retardant polymer and an impact modifier, the impact strength was lower than that of Examples 1 to 4, and the heat resistance was lowered.

As described above, the flame retardant polymer grafted with the polyurethane oligomer according to the present invention has excellent flame retardancy and impact strength by itself even without further mixing the impact modifier and the flame retardant, and has excellent scratch resistance, coating materials, optical It can be applied to a wide range of materials, for example, for exterior materials of electrical and electronic products.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (16)

(C) Polyurethane oligomer is grafted to the polymer containing 60 to 90 weight% of (A) (meth) acrylic-type monomers, and 10 to 40 weight% of (B) vinyl-group containing phosphorus monomers. According to claim 1, wherein the polyurethane oligomer (C) is grafted 1 to 10 parts by weight based on 100 parts by weight of the polymer containing the (meth) acrylic monomer (A) and the vinyl group-containing phosphorus monomer (B). A copolymer resin characterized by the above-mentioned. The copolymer resin according to claim 1, wherein the weight average molecular weight is 50,000 to 500,000 g / mol. The method of claim 1, wherein the (meth) acrylic monomer (A) (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hydroxy ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, At least one monomer selected from the group consisting of cyclohexyl (meth) acrylate, n-hexyl (meth) acrylate, glycidyl (meth) acrylate and (meth) acrylic acid; And The copolymer resin characterized by the combination of the (meth) acrylic-type monomer which has a hydroxyl group. The copolymer resin according to claim 1, wherein the vinyl group-containing phosphorus monomer (B) is selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4 and mixtures thereof: [Formula 1] [Formula 2]

[Formula 3] [Formula 4]

(In Formulas 1 to 4, R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are each independently a methyl group or an ethyl group, n is 0 or 1). The copolymer resin according to claim 1, wherein the vinyl group-containing phosphorus monomer (B) is dimethyl vinylphosphonate or dimethyl allylphosphonate. The copolymer resin according to claim 1, wherein the phosphorus content of the vinyl group-containing phosphorus monomer (B) is 15 to 30% by weight. The copolymer resin according to claim 1, wherein the polyurethane oligomer (C) is prepared by polymerizing diisocyanate and diol. The copolymer resin according to claim 8, wherein the diisocyanate is at least one selected from the group consisting of diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and butylene diisocyanate. The copolymer resin according to claim 8, wherein the diol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and polycarbonate diol. The copolymer resin according to claim 8, wherein the equivalent ratio of the diisocyanate and the diol is 1.0 to 3.0. Polymerizing a monomer mixture comprising (A) 60 to 90 wt% of (meth) acrylic monomer and 10 to 40 wt% of (B) vinyl group-containing phosphorus monomer to form a polymer; And (C) a method for producing a copolymer resin, comprising the step of grafting a polyurethane oligomer to the formed polymer. The method according to claim 12, wherein the polyurethane oligomer (C) is grafted 1 to 10 parts by weight based on 100 parts by weight of the polymer containing the (meth) acrylic monomer (A) and the vinyl group-containing phosphorus monomer (B). Method for producing a copolymer resin characterized in that. 13. The method of claim 12, wherein the polyurethane oligomer (C) is polymerized including diisocyanate and diol. 15. The method of claim 14, wherein the equivalent ratio of the diisocyanate and the diol is 1.0 to 3.0. The molded article manufactured using the copolymer resin in any one of Claims 1-11.