KR101134016B1 - High Heat-Resistant, Scratch-Resistant and Flameproof Thermoplastic Resin Composition - Google Patents

Abstract

 The high heat resistant scratch flame retardant thermoplastic resin composition of the present invention comprises (A) 10 to 98% by weight of a polycarbonate resin; (B) 1 to 85% by weight of ultra low molecular weight (meth) acrylic resin; (C) rubber modified aromatic vinyl copolymer resin 1 to 30% by weight; It comprises 1 to 30 parts by weight of a phosphorus-based flame retardant containing (D) a cyclic phosphazene oligomeric compound based on 100 parts by weight of the base resin containing (A) + (B) + (C). The resin composition of the present invention has excellent balance of physical properties of flame retardancy, heat resistance, surface impact strength and scratch resistance.

Polycarbonate resin, ultra low molecular weight (meth) acrylic resin, ultra low molecular weight (meth) acrylic resin, phosphazene flame retardant, heat resistance and scratch resistance

Description

High Heat-Resistant, Scratch-Resistant and Flameproof Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition excellent in scratch resistance. More specifically, the present invention introduces an ultra low molecular weight (meth) acrylic resin and a rubber-modified vinyl graft copolymer into a polycarbonate resin, and introduces a specific phosphorus flame retardant thereto, thereby providing properties of flame retardancy, heat resistance, impact resistance to scratch, and scratch resistance. The present invention relates to a thermoplastic resin composition having excellent balance.

Background of the Invention

Thermoplastic resins have lower specific gravity than glass or metal and have excellent physical properties such as excellent moldability and impact resistance. With the recent trend of low cost, large size, and light weight of electric and electronic products, plastic products are rapidly replacing the existing glass or metal areas, thereby expanding the use area from electric and electronic products to automobile parts. Accordingly, the function of the exterior material and the performance of the appearance become important, and the demand for flame retardancy due to scratch resistance from external impacts or scratches or safety problems against fire is also increasing. An approach that can be approached to achieve scratch resistance and flame retardancy simultaneously is to alloy polycarbonate (PC) resins and methacrylate-based resins, more preferably polymethylmethacrylate (PMMA).

Polycarbonate resin has excellent mechanical strength and is excellent in transparency, thermal stability, self-extinguishing and dimensional stability. It is widely used in electric and electronic products and automobile parts. It is easy to achieve flame retardancy with a small amount of flame retardant. However, the scratch resistance of the polycarbonate itself is not good in and around the pencil hardness B, there is a problem that can not achieve good scratch resistance with only polycarbonate resin.

On the other hand, in the case of polymethyl methacrylate resin having excellent scratch resistance property, the pencil hardness of the resin itself is very good as about 3H, but has a disadvantage in that it is very difficult to achieve flame retardancy with a conventional flame retardant. Therefore, it is possible to blend PC resins and PMMA resins to complementally improve scratch performance and flame retardant properties, which are mutually problematic.

However, since PC and PMMA resin are incompatible, there is a disadvantage in that each phase is separated even when melt kneading at a high temperature. In addition, since the refractive index of PC is 1.59 and the refractive index of PMMA is 1.49, the alloys of PC and PMMA show pearl color by scattering light, so it is difficult to color with high saturation and weld line during injection. ) Is very difficult to apply to the exterior of the electrical and electronic products.

In order to commercialize polycarbonate and (meth) acrylic resin, Korean Patent Publication No. 2004-0079118 discloses a method of improving compatibility by using a metal stearic acid ester to lower the molecular weight of polycarbonate during kneading. However, this method has the disadvantage that the mechanical properties are sharply lowered.

U. S. Patent No. 5,280, 070 discloses a process for producing transparent PC / PMMA Blend using syndiotactic polymethylmethacrylate in polycarbonate. However, commercially available syndiotyl polymethylmethacrylate resins have a disadvantage.

In addition, U.S. Patent No. 4,027,073 attempts to coat the resin surface in order to improve scratch resistance, but has a disadvantage of having to undergo an additional process.

Therefore, in order to solve the above problems, the present inventors have introduced ultra-low molecular weight (meth) acrylic resins into polycarbonate resins to improve compatibility and scratch resistance, and by introducing specific phosphorus flame retardants therein, flame retardance, heat resistance, It is to develop a thermoplastic resin composition having excellent balance of surface impact strength and scratch resistance.

An object of the present invention is to provide a scratch-resistant flame retardant thermoplastic resin composition excellent in heat resistance.

Another object of the present invention is to provide a thermoplastic resin composition having excellent balance of physical properties of flame resistance, heat resistance, surface impact strength and scratch resistance.

Still another object of the present invention is to provide a high heat resistant scratch flame retardant thermoplastic resin composition having improved compatibility between polycarbonate and acrylic resin.

Another object of the present invention is to improve the flame retardancy and heat resistance, to significantly improve the compatibility between the base resin and to improve the surface impact, which is also a practical impact, high heat-resistant scratch-resistant flame-retardant thermoplastic resin composition having a good appearance and scratch resistance It is to provide.

      Another object of the present invention is to provide a high heat-resistant scratch-resistant flame retardant thermoplastic resin composition excellent in compatibility with polycarbonate resin while reducing the cost by introducing an ultra-low molecular weight (meth) acrylic resin.

Still another object of the present invention is to provide a high heat resistant scratch flame retardant thermoplastic resin composition that can be manufactured into a plastic molded article.

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

Summary of the Invention

The present invention provides a high heat resistant scratch flame retardant thermoplastic resin composition. The composition comprises (A) 10 to 98% by weight of a polycarbonate resin; (B) 1 to 85% by weight of ultra low molecular weight (meth) acrylic resin; (C) rubber modified aromatic vinyl copolymer resin 1 to 30% by weight; It comprises 1 to 30 parts by weight of a phosphorus-based flame retardant containing (D) a cyclic phosphazene oligomeric compound based on 100 parts by weight of the base resin containing (A) + (B) + (C). In an embodiment, the base resin is (A) 60 to 90% by weight of a polycarbonate resin; (B) 5 to 35% by weight of ultra low molecular weight (meth) acrylic resin; And (C) 1 to 20% by weight of the rubber-modified aromatic vinyl copolymer resin.

The ultra-low molecular weight (meth) acrylic resin (B) preferably has a weight average molecular weight of 3,000 to 40,000. The ultra low molecular weight (meth) acrylic resin (B) may have a refractive index of 1.490 to 1.590.

In an embodiment, the ultra low molecular weight (meth) acrylic resin (B) has a linear structure.

The ultra low molecular weight (meth) acrylic resin (B) may be a copolymer of (B1) aromatic or aliphatic methacrylate with a monofunctional unsaturated monomer, (B2) a C ₁ -C ₁₀ alkyl (meth) acrylate polymer or a mixture thereof Can be. In specific embodiments, the ultra low molecular weight (meth) acrylic resin (B) may include (B1) 5 to 100 wt% of an aromatic or aliphatic methacrylate and 0 to 100 wt% of a polymer of 0 to 95 wt% of a monofunctional unsaturated monomer; And (B2) 0 to 100% by weight of C ₁ -C ₁₀ alkyl (meth) acrylate polymer polymerized with 5 to 100% by weight of methylmethacrylate and 0 to 95% by weight of monofunctional unsaturated monomer.

As the monofunctional unsaturated monomer, methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, acrylamides and methacrylamides, and the like can be used.

In an embodiment the (B2) C ₁ -C ₁₀ alkyl (meth) acrylate polymer is methyl methacrylate and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and their It may be a copolymer of an acrylic monomer selected from the group consisting of a mixture or a mixture thereof.

The rubber polymer is a group consisting of diene rubber, saturated rubber in which hydrogen is added to the diene rubber, isoprene rubber, chloroprene rubber, (meth) acrylic rubber, silicone rubber, and ethylene / propylene / diene monomer terpolymer (EPDM). One or more may be selected from.

In embodiments, the phosphorus flame retardant (D) is composed of 50-100% by weight of the (D1) cyclic phosphazene oligomeric compound and 0-50% by weight of the (D2) aromatic phosphate ester compound.

The resin composition may be an antidropping agent, an impact modifier, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a pigment, a dye, an inorganic additive, an antibacterial agent, an antistatic agent, a nucleating agent, a coupling agent. Fillers, plasticizers, surfactants, nucleating agents, coupling agents. It may further include additives such as plasticizers, lubricants, antibacterial agents, mold release agents, flame retardants.

Another aspect of the present invention provides a molded article molded from the resin composition. The molded article has a heat resistance of 100-130 ° C., measured by ASTM D1525 (load 5Kg, 50 ° C./hr), a 1.5 mm thickness flame retardance of V-0 according to UL 94 V, and a 3.2 mm thick surface impact strength (height). 0.95 m, 5 Kg) is nondestructive when evaluated.

Detailed Description of the Invention

(A) polycarbonate resin

The polycarbonate resin (A) according to the present invention can be prepared by reacting diphenols represented by the following formula (1) with phosgene or carbonate diester.

[Formula 1]

Wherein A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO _2-

Specific examples of the diphenol of the general formula (1) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, and 2,4-bis- (4-hydroxyphenyl)- 2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3 , 5-dichloro-4-hydroxyphenyl) -propane and the like. As the diphenol compound, compounds such as hydroquinone and resorcinol can be used. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols, such as hydroxyphenyl) -cyclohexane, are preferable, and 2, 2-bis- (4-hydroxyphenyl) propane also called bisphenol-A is especially preferable. The polycarbonate resin of the present invention has a weight average molecular weight (M _w ) of 10,000 to 200,000, preferably 15,000 to 80,000.

The structure of the polycarbonate resin may be linear or branched, and mixtures thereof may also be applied. In an embodiment, the branched polycarbonate may be prepared by adding 0.05 to 2 mol% of a tri- or more polyfunctional compound, such as a compound having a trivalent or more phenol group, based on the total amount of diphenols used for polymerization. Can be. Moreover, the said polycarbonate resin can be used individually or in mixture of 2 or more types from which molecular weight differs. In other embodiments, polyestercarbonate copolymer resins may also be used.

In the present invention, the polycarbonate resin (A) is used in 10 to 98% by weight of the base resin. The polycarbonate resin serves to facilitate imparting flame retardancy. Preferably it is 40 to 90% by weight, when applied in the above range, it is possible to obtain the balance of the flame retardancy and mechanical strength and scratch resistance. More preferably 50 to 80% by weight, most preferably 60 to 77% by weight.

(B) Ultra low molecular weight (meth) acrylic resin

The ultra low molecular weight (meth) acrylic resin (B) has an ultra low molecular weight of 3,000 to 40,000. In embodiments, the weight average molecular weight may be 10,000 to 35,000. In other embodiments the weight average molecular weight may be between 3,000 and 9,800.

The ultra low molecular weight (meth) acrylic resin may be polymerized by conventional bulk, emulsification and suspension polymerization methods. In addition, the ultra low molecular weight (meth) acrylic resin may be a homopolymer using one kind of (meth) acrylic monomer, or may be prepared from a copolymer using two or more kinds of (meth) acrylic monomers or a mixture thereof.

The ultra low molecular weight (meth) acrylic resin (B) may have a refractive index of 1.490 to 1.590. In one embodiment, the refractive index can be 1.495 to 1.590, and ultra high refractive index of 1.51 to 1.59 can be used.

It is preferable that the structure of the said ultra low molecular weight (meth) acrylic-type resin (B) has a linear structure.

The ultra low molecular weight (meth) acrylic resin (B) may be a copolymer of (B1) aromatic or aliphatic methacrylate with a monofunctional unsaturated monomer, (B2) a C ₁ -C ₁₀ alkyl (meth) acrylate polymer or a mixture thereof Can be. When the copolymer (B1) of an aromatic or aliphatic methacrylate and a monofunctional unsaturated monomer is used, the difference in refractive index with a polycarbonate resin is small and it can obtain more excellent transparency. When the C ₁ -C ₁₀ alkyl (meth) acrylate polymer (B2) is applied, excellent physical properties can be obtained while minimizing the manufacturing cost.

In an embodiment, the ultra low molecular weight (meth) acrylic resin (B) is (B1) 5 to 100% by weight of an aromatic or aliphatic methacrylate having a structure represented by Formula 1 or Formula 2 below and 0 to 95% by weight of a monofunctional unsaturated monomer. 0 to 100 weight percent polymer; And (B2) 0 to 100% by weight of C ₁ -C ₁₀ alkyl (meth) acrylate polymer polymerized with 5 to 100% by weight of methyl methacrylate and 0 to 95% by weight of monofunctional unsaturated monomer. In another embodiment, 0-100 wt% of a copolymer of (B1) 50-100 wt% of an aromatic or aliphatic methacrylate and 0-50 wt% of a monofunctional unsaturated monomer; And (B2) 0 to 100% by weight of C ₁ -C ₁₀ alkyl (meth) acrylate polymer polymerized with 50 to 100% by weight of methylmethacrylate and 0 to 50% by weight of monofunctional unsaturated monomer.

When the aromatic or aliphatic methacrylate is included at 5 wt% or more, the average refractive index of the polymerized ultra low molecular weight (meth) acrylic copolymer resin may be 1.495 or higher.

The aromatic or aliphatic methacrylate may be represented by the following formula (2) or (3).

[Formula 1]

Wherein m is an integer of 0-10, X is a cyclohexyl group, a phenyl group, a methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group Selected from the group consisting of

[Formula 2]

(Wherein m is an integer of 0-10, Y is oxygen (O) or sulfur (S), Ar is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group , Bromophenyl group, phenylphenyl group and benzylphenyl group).

Examples of the aromatic or aliphatic methacrylates include cyclohexyl methacrylate, phenoxy methacrylate, 2-ethylphenoxy methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethylthiophenyl methacrylate, 2-phenylethyl methacrylate, 3-phenylporophyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenyl Ethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexylphenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl methacrylate, 2- (3-chlorophenyl) ethyl methacrylate, 2- (4-chlorophenyl) ethyl meta To arcrelate, 2- (4-bromophenyl) Methyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, and methacrylic acid, such as 2- (4-benzylphenyl) ethyl methacrylate, and the like. These may be used alone or in combination of two or more.

The monofunctional unsaturated monomer is not particularly limited, and methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, acrylamides and methacrylamides, and the like may be used. Specific examples include methacrylic acid esters including methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate as the monofunctional unsaturated monomers; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; Esters containing hydroxy groups, including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and monoglycerol acrylate; Acrylamide and methacrylamide, and the like, but are not necessarily limited thereto. These may be used alone or in combination of two or more.

The C ₁ -C ₁₀ alkyl (meth) acrylate polymer (B2) is methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl Homopolymers, copolymers of (meth) acrylic monomers selected from the group consisting of methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof It may be a mixture.

In the present invention, the ultra low molecular weight (meth) acrylic resin (B) may be alloyed with a polycarbonate resin to reduce the refractive index difference and increase compatibility. In addition, the compatibility is further increased by the ultra low molecular weight of less than 40,000 weight average molecular weight.

In the present invention, the ultra-low molecular weight (meth) acrylic resin (B) is used in 1 to 85% by weight of the basic resin, preferably 5 to 50% by weight. Most preferably 10 to 35% by weight. When used in more than 10% by weight, the scratch resistance is increased, and when used in excess of 85% by weight, the impact and mechanical properties can be reduced and the flame retardancy is sharply reduced.

(C) rubber modified aromatic vinyl copolymer resin

The rubber-modified aromatic vinyl copolymer resin (C) according to the present invention is a polymer in which a rubbery polymer is dispersed and present in a particle form in a matrix (continuous phase) made of an aromatic vinyl polymer.

In one embodiment, the rubber-modified aromatic vinyl copolymer resin (C) is composed of 20 to 50% by weight of rubbery polymer units, 40 to 60% by weight of aromatic vinyl units and 10 to 30% by weight of vinyl cyanide units.

The rubber-modified aromatic vinyl copolymer resin is polymerized by adding an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer optionally to the rubbery polymer. Such rubber-modified aromatic vinyl copolymer resins can be produced by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, and graft copolymer resins and copolymer resins are usually produced by mixed extrusion. In the case of the bulk polymerization, the rubber modified aromatic vinyl copolymer resin is produced by only one step reaction without producing the graft copolymer resin and the copolymer resin separately, but in any case, the final rubber modified aromatic vinyl copolymer resin (C) Among the components, the rubber content is most suitably about 1 to about 30% by weight. The particle size of the rubber is about 0.1 to about 6.0 μm in Z-average, and in order to obtain desirable physical properties, it is more preferable that the rubber particle size is about 0.25 to about 3.5 μm in Z-average.

The rubber-modified aromatic vinyl copolymer resin used in the present invention may be prepared by using graft copolymer resin alone or in combination with a graft copolymer resin and a copolymer resin. desirable.

(C ₁ ) graft copolymer resin

The graft copolymer resin of the present invention is obtained by graft copolymerization of a rubbery polymer, an aromatic vinyl monomer, a monomer copolymerizable with an aromatic vinyl monomer, and a monomer which selectively gives processability and heat resistance.

Examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and acrylic rubbers such as saturated rubbers, isoprene rubbers and polybutylacrylic acid hydrogenated with the diene rubbers. Rubber and ethylene-propylene-diene monomer terpolymer (EPDM); Among these, especially diene rubber is preferable and butadiene rubber is more preferable. The amount of the rubbery polymer is suitably about 5 to about 65% by weight of the total weight of the graft copolymer resin (C ₁ ). The average size of the rubber particles is preferably in the range of about 0.1 to about 4 ㎛ in consideration of impact strength and appearance.

The aromatic vinyl monomer in the graft copolymerizable monomer mixture may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, Dibromostyrene, vinyl naphthalene, or the like may be used, but is not necessarily limited thereto. Of these, styrene is most preferred. The aromatic vinyl monomer may be graft copolymerized using about 34 to about 94 wt% of the total weight of the graft copolymer resin (C ₁ ).

The graft copolymer resin (C ₁ ) of the present invention may introduce at least one monomer copolymerizable with an aromatic vinyl monomer. As the monomer to be introduced, vinyl cyanide such as acrylonitrile and unsaturated nitrile based compounds such as ethacrylonitrile and methacrylonitrile are preferable, and may be used alone or in combination of two or more thereof. The monomer is copolymerized using about 1 to about 30% by weight of the total weight of the graft copolymer resin (C ₁ ).

Examples of the monomer for imparting the processability and heat resistance include acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide. The amount of monomer added is from about 0 to about 15 weight percent of the total weight of the graft copolymer resin (C ₁ ).

(C ₂ ) copolymer resin

The copolymer resin (C ₂ ) is prepared according to the monomer ratio and compatibility of the components of the graft copolymer resin (C ₁ ) excluding rubber, monomers copolymerizable with aromatic vinyl monomers, aromatic vinyl monomers, and optional It is obtained by adding and copolymerizing a monomer giving processability and heat resistance.

As the aromatic vinyl monomer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, monochlorostyrene, dichlorostyrene, dibromostyrene, etc. may be used. It is not necessarily limited thereto. Of these, styrene is most preferred. In the present invention, the aromatic vinyl monomer is about 60 to about 90% by weight of the total weight of the copolymer resin (C ₂ ) to obtain a copolymer resin.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include a vinyl cyanide compound such as acrylonitrile or an unsaturated nitrile compound such as ethacrylonitrile or methacrylonitrile, and may be used alone or in combination of two or more thereof. have. The content of the copolymerizable monomer with the aromatic vinyl monomer is about 10 to about 40% by weight of the total weight of the copolymer resin (C ₂ ).

Acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, etc. are mentioned as a monomer for providing the said processability and heat resistance. The content of the monomer added at the time of copolymerization to impart processability and heat resistance is about 0 to about 30% by weight of the total weight of the copolymer resin (C ₂ ).

Examples of the rubber-modified aromatic vinyl copolymer resin (C) used in the present invention include acrylonitrile-butadiene-styrene copolymer resins (ABS resins) and acrylonitrile-ethylenepropylene rubber-styrene copolymer resins (AES resins). And acrylonitrile-acryl rubber-styrene copolymer resin (AAS resin).

The rubber-modified aromatic vinyl copolymer resin (C) used in the present invention is about 10 to about 100% by weight of the graft copolymer resin (C ₁ ) and about 0 to about 90% by weight of the copolymer resin (C ₂ ). Use a mixture of ratios. In an embodiment, the rubber-modified aromatic vinyl copolymer resin (C) is composed of about 55 to about 90 wt% of the graft copolymer resin (C ₁ ) and about 10 to about 45 wt% of the copolymer resin (C ₂ ). In another embodiment, the rubber-modified aromatic vinyl copolymer resin (C) may be composed of 15 to 50 wt% of the graft copolymer resin (C ₁ ) and 50 to 85 wt% of the copolymer resin (C ₂ ).

Rubber-modified aromatic vinyl copolymer resin (C) of the present invention is used in 1 to 30% by weight, preferably 1 to 20% by weight of the base resin.

(D) phosphorus flame retardant

The phosphorus flame retardant (D) of the present invention includes a cyclic phosphazene oligomeric compound.

The cyclic phosphazene oligomeric compound (D1) is a compound represented by the following formula (4) or a mixture thereof.

[Formula 4]

_Wherein R ₁ is a substituent selected from C ₁ -C ₁₀ alkyl group, C _6-20 aryl group, C ₁ -C ₁₀ alkyl substituted C _6-20 aryl group, aralkyl group, alkoxy group, aryloxy group, amino group or hydroxy group , k and m are integers of 0-10, R ₂ is C ₆ -C ₃₀ dioxyaryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₃₀ dioxyaryl group derivative, n is the number average degree of polymerization The average value of n is 0.3 to 3.

The alkoxy group or aryloxy group of Formula 4 may be substituted with an alkyl group, an aryl group, an amino group, or a hydroxyl group.

In embodiments, the (D1) cyclic phosphazene oligomeric compound may be R ₁ is a methyl group, ethyl group, propyl group, phenyl group or phenoxy group. The values of k and m are preferably 1-5, more preferably 1-3. R ₂ is preferably derived from resorcinol. In another embodiment, the cyclic phosphazene oligomeric compound (D1) is 40-75 wt% of a compound having a value of n in Formula 4, 10-40 wt% of a compound having a value of n, and a value of n is 2 It may be a mixture of 0.1-10% by weight of the phosphorus compound, 1-15% by weight of the compound of the value of n or more.

In a specific embodiment, the phosphorus-based flame retardant (D) may be used alone (D1) cyclic phosphazene oligomer-type compound, or may be mixed with (D2) aromatic phosphate ester compound.

In an embodiment, the (D2) aromatic phosphate ester compound may be represented by the following Formula 5.

[Chemical Formula 5]

In the above formula, R _1, R _2, R _4, R ₅ are each independently a C ₆ -C ₂₀ aryl group or C ₁ -C ₁₀ Alkyl-substituted aryl group, R ₃ is resorcinol, hydroquinol, bisphenol- A, or one derived from a dialcohol of bisphenol-S, n is 0-5.

In the aromatic phosphate ester compound (D2), when i) n is 0, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trigylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, Tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate and the like, and ii) when n is 1, resorcinolbis (diphenylphosphate), hydroquinolbis (Diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis (2,6-diarybutyl phenyl phosphate), hydroquinol bis (2,6-dimethylphenyl phosphate), and the like; iii) When n is 2 or more, it may exist in the form of a mixture in oligomeric form. All or a mixture of two or more of the above-mentioned compounds are applicable.

In the present invention, in addition to the aromatic phosphate ester compound (D2) represented by the formula (5), phosphonate (Phosphonate), phosphinate (Phosphinate), phosphine oxide (Phosphine Oxide), phosphazene (Phosphazene) or metal salts thereof This can be applied.

The phosphorus flame retardant (D) of the present invention may be used in an amount of 1 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 7 to 20 parts by weight, based on 100 parts by weight of the base resin. In one embodiment, the cyclic phosphazene oligomeric compound (D1) may be used in an amount of 7 to 20 parts by weight, and an aromatic phosphate ester compound (D2) may be used in an amount of 6 parts by weight or less based on 100 parts by weight of the base resin. When the cyclic phosphazene oligomeric compound (D1) and the aromatic phosphate ester compound (D2) are applied together, the content of the cyclic phosphazene oligomeric compound (D1) is used more than that of the aromatic phosphate ester compound (D2). It is desirable to.

In an embodiment, the phosphorus flame retardant (D) is composed of 50-100% by weight of the (D1) cyclic phosphazene oligomeric compound and 0-50% by weight of the (D2) aromatic phosphate ester compound. Preferably it consists of 60-100 weight% of (D1) cyclic phosphazene oligomeric compound, and 0-40 weight% of (D2) aromatic phosphate ester type compound. More preferably, it consists of 70-100 weight% of (D1) cyclic phosphazene oligomeric compound, and 0-30 weight% of (D2) aromatic phosphate ester type compound.

In the thermoplastic resin manufacturing method of the present invention, antidropping agents such as polytetrafluoroethylene, impact modifiers, antioxidants, plasticizers, heat stabilizers, light stabilizers, compatibilizers, pigments, dyes, inorganic additives, antibacterial agents, and electrostatic agents Inhibitors, nucleating agents, coupling agents. Fillers, plasticizers, surfactants, nucleating agents, coupling agents. Additives, such as a plasticizer, a lubricating agent, an antibacterial agent, a mold release agent, and a flame retardant, can be used. The additives may be applied alone or by mixing two or more kinds. The inorganic additives include glass fibers, silica, talc, ceramics, and the like, and their content is suitably 0 to 50 parts by weight based on 100 parts by weight of the base resin.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, after mixing the components of the present invention and optionally other additives simultaneously, they can be melt extruded and produced in pellet form in an extruder, which can be used to produce plastic injection and compression molded articles. .

This invention provides the molded article which shape | molded the said resin composition. In one embodiment, the molded article has a heat resistance of 100-130 ° C. as measured by ASTM D1525 (load 5Kg, 50 ° C./hr), a 1.5 mm thickness flame retardancy of V 94 according to UL 94 V, and a 3.2 mm thickness plane. It is nondestructive when assessing impact strength (height 0.95 m, 5 Kg).

The composition of the present invention can be used for molding a variety of products, in particular for electrical and electronic products such as the housing of TVs and office automation equipment.

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

Example

The specification of each component used in the following Example and the comparative example is as follows.

(A) Polycarbonate resin (PC): Panlite L-1225 Grade of Teijin, Japan was used.

(B) Ultra low molecular weight (meth) acrylic resin

(B1) Ultra low molecular weight aromatic methacrylate copolymer

      30 wt% of phenyl methacrylate monomer having a refractive index of 1.570 and 70 wt% of methyl methacrylate monomer were prepared by a conventional suspension polymerization method, and the prepared copolymer had a refractive index of 1.515 and a weight average molecular weight of 30,000. .

(B2) Ultra low molecular weight alkyl (meth) acrylate polymer

      Methyl methacrylate monomer was prepared by the conventional suspension polymerization method, and the weight average molecular weight was 13,000.

       (B3) High molecular weight (meth) acrylic resin

IH830 Grade (molecular weight 90,000 to 95,000) was used as the PMMA resin of LG MMA.

(C) Rubber modified vinyl graft copolymer

50 parts by weight of butadiene rubber latex was added to the reactor on a solid basis, and then 36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water were added, and 1.0 parts by weight of potassium oleate and cumene hydroperoxide were added to the total solids. 0.4 parts by weight, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of sodium pyrophosphate, and maintained at 75 ° C. for 5 hours to complete the reaction. Copolymer resin latex was prepared, and sulfuric acid was coagulated by adding 0.4 parts by weight to the solids of the resin to prepare a powder.

(D1) Cyclic phosphazene oligomeric compound

In formula (4), R ₁ is a phenoxy group, k and m are 1 or 2, n is 0, 66.5 wt%, R ₁ is a phenoxy group, R ₂ is derived from resorcinol, and k and m are 20.3 wt% with a value of 1 or 2, n of 1, R ₁ is a phenoxy group, R ₂ is derived from resorcinol, the value of k and m is 1 or 2, and the value of n is 2 4.9% by weight, and an oligomeric compound of cyclic phosphazene comprising 8.3% by weight of R ₁ is a phenoxy group, R ₂ is derived from resorcinol, the value of k and m is 1 or 2 and the value of n is at least 3 A mixture of was used.

(D2) Aromatic Phosphate Ester Compounds

Bisphenol A bis (diphenyl phosphate) was applied to CR-741 Grade manufactured by Daihachi Chemical in Japan.

(E) Anti-dripping agent (PTFE): Teflon (trade name) 7AJ of Dupont, USA was used.

Examples 1-13 and Comparative Examples 1-4

Each of the components was added in an amount as described in Table 1-3, and then extruded in a twin screw extruder at a temperature range of 220-260 ° C. to prepare pellets. The prepared pellets were dried at 80 ° C for 3 hours and then injected at 8 oz injection machine under molding temperature of 250 ° C and mold temperature of 60 ° C to prepare specimens. Heat resistance, flame retardancy, surface impact and scratch resistance were as follows. Measured.

Property evaluation method

(1) Heat resistance: It was measured under the load of 5kg weight and 50 ℃ / hr by the evaluation method specified in ASTM D1525.

(2) Flame retardancy: Flame retardancy for 1.5 mm thickness was measured according to the UL 94 V flame retardant regulations.

(3) Surface impact strength: The specimen surface was evaluated as fracture / nondestructive by dropping a 5 kg weight at 0.95 m for a 3.2 mm thick specimen.

(4) Scratch resistance: measured by BSP (Ball-type Scratch Profile) test. The BSP test was performed by applying a 100 mm × 100 mm × 3.2 mm resin specimen surface with a 0.7 mm diameter spherical metal tip and a 10-20 mm scratch at a speed of 1000 mm and 75 mm / min. Scratch width, which is a measure of scratch resistance, was measured by measuring the profile of the scratch applied by the contact surface profile analyzer (XP-1) of the sheet) by a surface scan using a metal stylus tip having a diameter of 2 μm. The unit is μm.

As shown in Tables 1 and 3, as the content of the (D1) cyclic phosphazene oligomer-type compound compared to the content of the (D2) aromatic phosphate ester compound, the heat resistance increases, the flame retardancy also increases. In addition, it can be seen that the scratch resistance increases as the content of (A) ultra low molecular weight (meth) acrylic resin is increased compared to the content of (A) polycarbonate resin, and scratch resistance variation between (B1) and (B2) has not been confirmed. It can be seen that. And, as shown in Comparative Example 4, the surface impact strength of 5.9J when applying a high molecular weight PMMA without incompatibility, the surface impact strength was all 46.55J or more when the ultra-low molecular weight (meth) acrylic resin is applied. Therefore, it was confirmed that the compatibility is excellent when the ultra low molecular weight PMMA or ultra low molecular weight PMMA-co-PhMA copolymer is applied.

The present invention improves flame retardancy and heat resistance, significantly improves compatibility between base resins, improves surface impact as a practical impact, and provides a high heat-resistant scratch-retardant thermoplastic resin composition having good appearance and scratch resistance. Have

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 (17)

(A) 10 to 98% by weight of polycarbonate resin; (B) 1 to 85% by weight of an ultra low molecular weight (meth) acrylic resin having a weight average molecular weight of 3,000 to 40,000; (C) rubber modified aromatic vinyl copolymer resin 1 to 30% by weight; Based on 100 parts by weight of the base resin containing the (A) + (B) + (C), (D) 1 to 30 parts by weight of a phosphorus flame retardant comprising a cyclic phosphazene oligomeric compound; Wherein the ultra low molecular weight (meth) acrylic resin (B) is (B1) 5 to 100% by weight of an aromatic or aliphatic methacrylate having the structure of Formula 1 or Formula 2 and 0 to 95% by weight of a monofunctional unsaturated monomer. A high heat resistant scratch flame retardant thermoplastic resin composition, characterized in that it is a polymer or a mixture of said polymer (B1) and (B2) C ₁ -C ₁₀ alkyl (meth) acrylate polymer: [Formula 1]

Wherein m is an integer of 0-10, X is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group It is selected from the group consisting of; [Formula 2]

Wherein m is an integer of 0 to 10, Y is oxygen (O) or sulfur (S), Ar is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group , Bromophenyl group, phenylphenyl group and benzylphenyl group. delete The scratch resistant flame retardant thermoplastic resin composition of claim 1, wherein the ultra low molecular weight (meth) acrylic resin (B) has a refractive index of 1.490 to 1.590. The high heat resistance scratch flame retardant thermoplastic resin composition according to claim 1, wherein the ultra low molecular weight (meth) acrylic resin (B) has a linear structure. The method according to claim 1, wherein the C ₁ -C ₁₀ alkyl (meth) acrylate polymer (B2) is characterized in that the polymerization of 5 to 100% by weight of methyl methacrylate and 0 to 95% by weight of monofunctional unsaturated monomer Heat-resistant scratch flame retardant thermoplastic resin composition. 6. The monofunctional unsaturated monomer according to claim 1 or 5, wherein the monofunctional unsaturated monomer is selected from the group consisting of methacrylic acid esters including methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; Esters containing hydroxy groups, including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and monoglycerol acrylate; High heat resistance scratch-retardant thermoplastic resin composition, characterized in that at least one selected from the group consisting of acrylamide and methacrylamide. The method of claim 1, wherein the (B2) C ₁ -C ₁₀ alkyl (meth) acrylate polymer is methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, hexyl methacrylate Homopolymers of (meth) acrylic monomers selected from the group consisting of latex, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof, High heat-resistant scratch-retardant thermoplastic resin composition, characterized in that the copolymer or a mixture thereof. The method of claim 1, wherein the (C) rubber-modified aromatic vinyl copolymer resin is characterized in that (C ₁ ) graft copolymer resin 10 to 100% by weight and (C ₂ ) copolymer resin 0 to 90% by weight Heat-resistant scratch-retardant thermoplastic resin composition. The method according to claim 8, wherein the (C ₁ ) graft copolymer resin is 5 to 65% by weight of the rubbery polymer, 34 to 94% by weight of the aromatic vinyl monomer and 1 to 30% by weight of the monomer copolymerizable with the aromatic vinyl monomer It is a graft polymerized copolymer, and the (C ₂ ) copolymer resin is a copolymer of 60 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer. Scratch flame retardant thermoplastic resin composition. 10. The rubbery polymer according to claim 9, wherein the rubbery polymer is a diene rubber, a saturated rubber in which hydrogen is added to the diene rubber, an isoprene rubber, a chloroprene rubber, a (meth) acrylic rubber, a silicone rubber, and an ethylene / propylene / diene monomer terpolymer High heat resistance scratch-retardant thermoplastic resin composition, characterized in that at least one selected from the group consisting of (EPDM). The high heat resistance flame resistance of claim 1, wherein the phosphorus flame retardant (D) is composed of 50-100% by weight of (D1) cyclic phosphazene oligomeric compound and 0-50% by weight of (D2) aromatic phosphate ester compound. Scratch flame retardant thermoplastic resin composition. 12. The high heat resistance scratch flame retardant thermoplastic resin composition according to claim 11, wherein the (D1) cyclic phosphazene oligomeric compound is a compound represented by the following Chemical Formula 4 or a mixture thereof: [Formula 4]

_Wherein R ₁ is a substituent selected from C ₁ -C ₁₀ alkyl group, C _6-20 aryl group, C ₁ -C ₁₀ alkyl substituted C _6-20 aryl group, aralkyl group, alkoxy group, aryloxy group, amino group or hydroxy group , k and m are integers of 0-10, R ₂ is C ₆ -C ₃₀ dioxyaryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₃₀ dioxyaryl group derivative, n is the number average degree of polymerization The average value of n is 0.3 to 3. 12. The high heat resistant scratch flame retardant thermoplastic resin composition of claim 11, wherein the (D2) aromatic phosphate ester compound is represented by the following Formula: [Chemical Formula 5]

In the above, R _1, R _2, R _4, R ₅ are each independently an aryl group which is C ₆ -C ₂₀ or an aryl group which is substituted with C ₁ -C ₁₀ alkyl, R ₃ is resorcinol, hydroquinol, bisphenol -A, or one derived from a dialcohol of bisphenol-S, n is 0-5. According to claim 1, wherein the base resin (A) 60 to 90% by weight of a polycarbonate resin; (B) 5 to 35% by weight of ultra low molecular weight (meth) acrylic resin; And (C) 1 to 20% by weight of rubber-modified aromatic vinyl copolymer resin. The method of claim 1, wherein the resin composition is an antidropping agent, impact modifier, antioxidant, plasticizer, thermal stabilizer, light stabilizer, compatibilizer, pigment, dye, inorganic additive, antibacterial agent, antistatic agent, nucleating agent, coupling agent. A high heat resistant scratch flame retardant thermoplastic resin composition further comprising an additive selected from the group consisting of fillers, surfactants, lubricants, mold release agents, flame retardants and mixtures thereof. The molded article molded from the resin composition of any one of Claims 1, 3-5, and 7-15. The molded article according to claim 16, wherein the molded article has a heat resistance of 100 to 130 ° C as measured by ASTM D1525 (load 5Kg, 50 ° C / hr), a 1.5 mm thickness flame retardancy of V94 according to UL 94 V, and 3.2 mm. A molded article characterized by nondestructive evaluation in thickness surface impact strength (height 0.95 m, 5 Kg).