WO2014088153A1 - (metha)acrylic copolymer, and thermoplastic resin comprising same - Google Patents

Abstract

The (metha)acrylic copolymer of the present invention contains a phosphorus-containing heterocyclic group and a biphenyl group. The (metha)acrylic copolymer of the present invention is a copolymer of a monomer mixture comprising: (A) a phosphoric (metha)acrylic monomer comprising a phosphorus-containing heterocyclic group; (B) a biphenyl group-containing (metha)acrylic monomer having a refractive index of approximately 1.580 to approximately 1.700; and (C) an unsaturated monomer. The (metha)acrylic copolymer comprises the (metha)acrylic monomer having a high refractive index and the phosphoric (metha)acrylic monomer having a high refractive index, thus improving the refractive index and obtaining flame retardancy, transparency, scratch resistance, and environmentally friendly properties.

Description

(Meth) acrylic copolymer and thermoplastic resin containing same

The present invention relates to a (meth) acrylic copolymer and a thermoplastic resin comprising the same. More specifically, the present invention introduces a high refractive index (meth) acrylic monomer and a high refractive index phosphorus (meth) acrylic monomer to improve refractive index and have a high refractive index (meth) acrylic air having flame retardancy, transparency, scratch resistance, and environmental friendliness. It relates to a thermoplastic resin having excellent flame resistance, heat resistance, scratch resistance and eco-friendliness, including a copolymer and a (meth) acrylic copolymer and a polycarbonate resin.

Thermoplastic resins have a lower specific gravity than glass or metal and have excellent physical properties such as formability and impact resistance. Recently, due to the trend of low cost, large size, and light weight of electric and electronic products, plastic products using thermoplastic resins are rapidly replacing the areas where glass or metal was used, and are expanding the use area from electric and electronic products to automobile parts. Accordingly, the function of the exterior and the performance of the appearance have become important, and in particular, the demand for transparent resins is increasing due to the high thickness of electrical and electronic products and the change in design concept. Accordingly, there is an increasing demand for a functional transparent material that provides functionality such as scratch resistance and flame retardancy to existing transparent resins.

Polycarbonate resin is very excellent in mechanical strength and flame retardancy, excellent transparency and weather resistance, very good impact resistance, thermal stability, etc., but has a disadvantage of very poor scratch resistance.

Existing transparent scratch-resistant material is an acrylic resin represented by polymethyl methacrylate (PMMA). The PMMA is excellent in transparency, weather resistance, mechanical strength, surface gloss, adhesive strength, and the like, in particular, very excellent scratch resistance, but has a disadvantage that the impact resistance and flame retardancy is very weak.

In order to increase the impact resistance while maintaining the excellent transparency of the PMMA, there is a method of using an acrylic impact modifier with the same refractive index as the PMMA. However, the acrylic impact modifiers have a lower impact efficiency than butadiene-based impact modifiers, and do not have sufficient impact resistance. In addition, there is a method of adding a flame retardant to reinforce the flame retardancy of PMMA, but not only is it difficult to obtain sufficient flame retardancy, the physical properties such as heat resistance, impact resistance, etc. may be lowered, and the thermal stability There is a problem of deterioration. Accordingly, there is no report of flame retardant to transparent acrylic resin alone.

In order to overcome the above problems, a method of copolymerizing a flame retardant acrylic monomer in the production of PMMA resin has been developed. However, conventionally developed flame-retardant acrylic monomers have a disadvantage in increasing the refractive index, it is difficult to express the flame retardancy by the addition of a small amount of flame retardant, there is a disadvantage that the mechanical properties including impact properties when the flame retardant is added. .

In addition, in order to overcome the above problems and at the same time to achieve mechanical properties including impact resistance and scratch resistance performance, a method of manufacturing PC / PMMA resin by mixing polycarbonate and acrylic resin, preferably PMMA, etc. has been developed. It became. In addition, in order to manufacture a highly compatible PC / PMMA resin, a high scratch resistance polycarbonate and an acrylic alloy resin applying an acrylic copolymer having a high refractive index has been developed. However, a copolymer having high refractive index monomers, which have been developed in the related art, has a limitation in increasing refractive index or heat resistance, and the polycarbonate and acrylic alloy resins are difficult to express flame retardancy by adding a small amount of flame retardant, and heat resistant when a flame retardant is added. There is a disadvantage that the mechanical properties, including the figure is lowered.

An object of the present invention is to provide a (meth) acrylic copolymer having high refractive index and excellent flame retardancy.

Another object of the present invention is to provide an environmentally friendly flame retardant (meth) acrylic copolymer having excellent transparency, scratch resistance and impact resistance.

Still another object of the present invention is to provide a thermoplastic resin excellent in flame retardancy and scratch resistance.

Still another object of the present invention is to provide an environmentally friendly flame retardant scratch resistant thermoplastic resin having excellent transparency and impact resistance.

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

One aspect of the present invention relates to a (meth) acrylic copolymer. The (meth) acrylic copolymer contains a phosphorus containing heterocyclic group and a biphenyl group.

In a specific example, the (meth) acrylic copolymer may include (A) a phosphorus-based (meth) acrylic monomer including a phosphorus-containing heterocyclic group; (B) a biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700; And (C) a monomer mixture comprising unsaturated monomers.

Preferably, the (meth) acrylic copolymer is about 1 to about 50 wt% of the phosphorus (meth) acrylic monomer (A), about 1 to about 30 wt% of the biphenyl group-containing (meth) acrylic monomer (B) and the And about 20 to about 98 weight percent of unsaturated monomers (C).

Preferably, the phosphorus (meth) acrylic monomer (A) may be represented by the following Chemical Formula 1:

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrocarbon group of 1 to 20 carbon atoms, R ₃ and R ₄ are each independently a substituted or unsubstituted cyclic hydrocarbon group of 6 to 20 carbon atoms, m is an integer of 1-10, n is an integer of 0-5.

Preferably, the biphenyl group-containing (meth) acrylic monomer (B) may be represented by the following Chemical Formula 2:

[Formula 2]

In Formula 2, R ₅ is a hydrogen atom or a methyl group, R ₆ is a substituted or unsubstituted biphenyl group or a substituted or unsubstituted terphenyl group, x is an integer of 0 to 10.

Preferably, the unsaturated monomer (C) is alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allyl glycidyl ether; Glycidyl methacrylate; And styrene-based monomers.

Preferably, the monomer mixture may further include an alicyclic or aromatic (meth) acrylic monomer having a (D) refractive index of about 1.490 to about 1.579.

Preferably, the alicyclic or aromatic (meth) acrylic monomer (D) may be represented by the following Formula 3:

[Formula 3]

In Formula 3, R ₇ is a hydrogen atom or a methyl group, R ₈ is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X is an oxygen atom or Is a sulfur atom, y is an integer from 0 to 10, and Z is 0 or 1;

Preferably, the alicyclic or aromatic (meth) acrylic monomer (D) may comprise about 0 to about 30% by weight of the total (meth) acrylic copolymer.

Preferably, the (meth) acrylic copolymer may have a weight average molecular weight of about 5,000 to about 500,000 g / mol.

Preferably, the (meth) acrylic copolymer has a refractive index of about 1.510 to about 1.590 at a thickness of 2.5 mm, a flame retardancy measured according to UL94 of 3.2 mm thick, and is at least V2, and a specimen having a thickness of 2.5 mm ASTM D1003. The total light transmittance measured according to the present invention may be about 85% or more.

Preferably, the (meth) acrylic copolymer is a flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additive, electrostatic It may further comprise one or more of inhibitors, pigments and dyes.

Another aspect of the invention relates to a thermoplastic resin. The thermoplastic resin is (A) polycarbonate resin; And (B) the (meth) acrylic copolymer.

In embodiments, the thermoplastic resin comprising about 50 to about 99% by weight of the polycarbonate resin (A), and about 1 to about 50% by weight of the (meth) acrylic copolymer (B).

The thermoplastic resin further comprises (C) a rubber-modified vinyl-based graft copolymer resin.

Preferably, the rubber-modified vinyl-based graft copolymer resin (C) has a structure in which a unsaturated monomer is grafted to a rubber core to form a shell, and the unsaturated monomer is an alkyl (meth) acrylate having 1 to 12 carbon atoms and an acid. An anhydride and the thermoplastic resin containing 1 or more types of a C1-C12 alkyl or phenyl-substituted maleimide.

In an embodiment, the thermoplastic resin further comprises (D) a phosphorus-based flame retardant.

In embodiments, the thermoplastic resin may be a flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additive, antistatic agent, pigment And at least one of dyes.

In an embodiment, the thermoplastic resin has a thickness of 3.2 mm and has a flame retardancy of at least V2 measured according to UL94, and a scratch width of about 180 to about 300 by a Balltype Scratch Profile Test. It is a micrometer and a pencil hardness is 2B-3H, The thermoplastic resin characterized by the above-mentioned.

The present invention includes a phosphorus (meth) acrylic monomer containing a phosphorous heterocyclic group, a biphenyl group-containing (meth) acrylic monomer, and the like, and have a high refractive index and excellent flame retardancy, and have transparency and scratch resistance. And an environmentally friendly flame retardant thermoplastic (meth) acrylate copolymer having excellent impact resistance. In addition, the present invention comprises a high refractive index (meth) acrylic copolymer and a polycarbonate resin prepared by applying the phosphorus-based (meth) acrylic monomer containing the phosphorus-containing heterocyclic group, excellent flame retardancy, transparency, heat resistance, The invention has the effect of providing a thermoplastic resin having scratch resistance, impact resistance and environmental friendliness. The (meth) acrylate copolymer and the thermoplastic resin are excellent in compatibility with the polycarbonate resin due to the high refractive index, can overcome the problems of transparency and coloring deterioration when blending, and at the same time can impart flame retardancy. It is also useful for various electric and electronic parts or automobile parts.

Hereinafter, the present invention will be described in detail.

The (meth) acrylate copolymer according to the present invention contains a phosphorus-containing heterocyclic group and a biphenyl group, and in one embodiment, a phosphorus-based (meth) acryl-based compound containing a phosphorus-containing heterocyclic group. A copolymer of a monomer mixture comprising a monomer, a biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700, and an unsaturated monomer.

Unless otherwise stated herein, "(meth) acryl" means that both "acryl" and "methacryl" are possible. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

Phosphorus-based (meth) acrylic monomers containing a phosphorous heterocyclic group used in the present invention have a higher refractive index than methyl methacrylate, for example, may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrocarbon group having 1 to 20 carbon atoms, for example, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, C6- C20 arylene group, preferably C1-C10 linear, branched or cyclic alkylene group, C6-C10 arylene group, more preferably C1-C4 linear alkylene group. R ₃ and R ₄ are each independently a substituted or unsubstituted cyclic hydrocarbon group having 6 to 20 carbon atoms, for example, a substituted or unsubstituted C6-C20 cycloalkyl group or an aryl group, preferably substituted or unsubstituted C6-C10 aryl group. m is an integer of 1-10, n is an integer of 0-5. Here, when n is 0, it represents a single bond, and the phosphorus containing heterocyclic group will form a hexagonal ring.

Unless otherwise specified in the specification of the present invention, "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group. In the "substituted", the hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, Carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, alkyl group of C1-C20, alkenyl group of C2-C20, alkynyl group of C2-C20, C1 A substituent of an alkoxy group of C20, an aryl group of C6-C30, an aryloxy group of C6-C30, a cycloalkyl group of C3-C30, a cycloalkenyl group of C3-C30, a cycloalkynyl group of C3-C30, or a combination thereof It means substituted by.

Specific examples of the phosphorus-based (meth) acrylic monomer may include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl (meth) acrylate, but are not limited thereto.

The refractive index of the phosphorus (meth) acrylic monomer may be, for example, about 1.580 to about 1.700, preferably about 1.590 to about 1.650. Within this range, a (meth) acrylic copolymer having a high refractive index can be obtained.

The content of the phosphorus (meth) acrylic monomer is about 1 to about 50% by weight, preferably about 5 to about 40% by weight of the total (meth) acrylic copolymer (monomer mixture). It is possible to obtain an excellent flame retardant (meth) acrylic copolymer without deteriorating heat resistance in the above range.

The biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700 used in the present invention has a refractive index of about 1.580 to about 1.700, and is characterized by containing a biphenyl structure.

The biphenyl group-containing (meth) acrylic monomer may be represented by, for example, the following Formula 2.

[Formula 2]

In Formula 2, R ₅ is a hydrogen atom or a methyl group, R ₆ is a substituted or unsubstituted biphenyl group or a substituted or unsubstituted terphenyl group, for example, an oligobiphenyl group, a metabiphenyl group, a parabiphenyl group, 2 , 6-terphenyl group, alloterphenyl group, metaterphenyl group, or paraterphenyl group. x is an integer of 0-10.

Examples of the biphenyl group-containing (meth) acrylic monomers include allobiphenyl methacrylate, metabiphenyl methacrylate, parabiphenyl methacrylate, 2,6-terphenyl methacrylate, alloterphenyl methacrylate, Metaterphenyl methacrylate, paraterphenyl methacrylate, 4- (4-methylphenyl) phenyl methacrylate, 4- (2-methylphenyl) phenyl methacrylate, 2- (4-methylphenyl) phenyl methacrylate, 2- (2-methylphenyl) phenyl methacrylate, 4- (4-ethylphenyl) phenyl methacrylate, 4- (2-ethylphenyl) phenyl methacrylate, 2- (4-ethylphenyl) phenyl methacrylate , 2- (2-ethylphenyl) phenyl methacrylate, and the like, but are not limited thereto. These can be used individually or in mixture of 2 or more types.

The content of the biphenyl group-containing (meth) acrylic monomer is about 1 to about 30% by weight, preferably about 5 to about 20% by weight of the total (meth) acrylic copolymer. Within this range, excellent high refractive index, transparency, and heat resistance physical property balance can be obtained, and it is easy to commercialize because of excellent compatibility with polycarbonate resin.

The unsaturated monomer used in the present invention is a monomer containing an unsaturated group, for example, alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allylglycidyl ether; Glycidyl methacrylate; Styrenic monomers, mixtures thereof, and the like. These can be applied individually or in mixture of 2 or more types.

Non-limiting examples of the unsaturated monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl Acrylate, acrylic acid, methacrylic acid, maleic anhydride, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, allyl Glycidyl ether, glycidyl methacrylate, styrene, alpha-methylstyrene, etc. can be illustrated. Preferably an alkyl (meth) acrylate having 1 to 8 carbon atoms, more preferably an alkyl (meth) acrylate having 1 to 4 carbon atoms can be used. In this case, better scratch resistance and transparency can be achieved.

In an embodiment, as the unsaturated monomer, it is possible to apply a mixture of methacrylate and acrylate. In this case, the ratio of methacrylate and acrylate may be about 10: 1 to about 50: 1. It may have better thermal stability and fluidity in the above range.

The content of the unsaturated monomer is about 20 to about 98% by weight, preferably about 40 to about 90% by weight of the total (meth) acrylic copolymer. Excellent scratch resistance, flowability, transparency and flame retardant balance of properties can be obtained in the above range.

The (meth) acrylic copolymer according to the present invention may further include an alicyclic or aromatic (meth) acrylic monomer having a refractive index of about 1.490 to about 1.579 as one of the monomers.

The alicyclic or aromatic (meth) acrylic monomer may be represented by the following formula (3).

[Formula 3]

In Formula 3, R ₇ is a hydrogen atom or a methyl group, R ₈ is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, for example, cyclohex It is a real group, a phenyl group, a methylphenyl group, methyl ethylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, and a benzylphenyl group. X is an oxygen atom or a sulfur atom, y is an integer of 0-10, Z is 0 or 1.

Non-limiting examples of the alicyclic or aromatic (meth) acrylic monomers include cyclohexyl methacrylate, phenoxy methacrylate, 2-ethylphenoxy methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethyl Thiophenyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl 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 methacrylate, 2- (4-bromophenyl) ethyl methacrylate, 2- (3-phenyl Phenyl) and the like can be given methacrylate, and 2- (4-benzylphenyl) ethyl methacrylate. These can be used individually or in mixture of 2 or more types.

The content of the cycloaliphatic or aromatic (meth) acrylic monomer is about 0 to about 30% by weight, preferably about 0 to about 25% by weight, more preferably about 5 to about 20, of the total (meth) acrylic copolymer. Weight percent. Excellent balance of refractive index and heat resistance in the above range can be obtained.

In addition, (meth) acrylic copolymers according to the present invention, if necessary, flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, commercialization Agents may further include one or more additives such as inorganic additives, antistatic agents, pigments and dyes. These additives may be added in the polymerization process, or may be added to the pelletization process (extrusion process, etc.) to be included in the copolymer, but the method and the addition amount thereof are not particularly limited.

Non-limiting examples of such antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydrophenyl) propionate, triethylene glycol-bis-3 (3-tertary-butyl-4 -Hydroxy-5-methylphenyl) propionate, 2,6-di-tert-butyl-4-methyl phenol, 2,2'-methylenebis (4-methyl-6-tert-butylbutyl phenol), tri ( 2,4-di-tert-butylphenyl) phosphite, normal-octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, disterylthiol dipropio Nate, lauthiol propionate methane, di-phenyl-isooctyl propionate, and the like.

The (meth) acrylic copolymer of the present invention may be prepared by conventional polymerization methods known in the copolymer production field, for example, bulk polymerization, emulsion polymerization, suspension polymerization, and the like. It may be prepared through a manufacturing method including the step of polymerizing.

In a preferred embodiment, the polymerization initiator is a radical polymerization initiator, the polymerization may be a suspension polymerization in consideration of the refractive index, etc., the suspension polymerization may be carried out in the presence of a suspension stabilizer and a chain transfer agent. That is, a radical polymerization initiator and a chain transfer agent are added to the monomer to prepare a reaction mixture, and the prepared reaction mixture is added to an aqueous solution in which a suspension stabilizer is dissolved to prepare a (meth) acrylic copolymer of the present invention (suspension polymerization). Can be. Here, the additive may be further added.

The polymerization initiator may be a conventional radical polymerization initiator known in the polymerization art, for example, octanoyl peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichloro Benzoyl peroxide, p-methylbenzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, azobis- (2,4-dimethyl) -valeronitrile, and the like, but are not limited thereto. . These can be used individually or in mixture of 2 or more types. The polymerization initiator may be included in an amount of about 0.01 to about 10 parts by weight, preferably about 0.02 to about 5 parts by weight, based on 100 parts by weight of the monomer mixture.

The chain transfer agent may be used to control the weight average molecular weight of the (meth) acrylate copolymer and to improve thermal stability. The weight average molecular weight can be controlled by the content of the polymerization initiator contained in the monomer. However, when the polymerization reaction is stopped by the chain transfer agent, the end of the chain becomes the second carbon structure. This is stronger in bond strength than the ends of the chain with double bonds produced when no chain transfer agent is used. Therefore, the addition of the chain transfer agent can improve the thermal stability, and eventually improve the optical properties of the (meth) acrylate copolymer.

As the chain transfer agent, conventional chain transfer agents known in the polymerization art may be used. For example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, isopropyl Alkyl mercaptans in the form of CH ₃ (CH ₂ ) _n SH (n is an integer from 1 to 20) including mercaptans, n-amyl mercaptans, and the like; Halogen compounds including carbon tetrachloride and the like; And aromatic compounds including alpha methylstyrene dimer or alpha ethylstyrene dimer, and the like, but are not limited thereto. These can be applied individually or in mixture of 2 or more types. Generally, the amount of the chain transfer agent varies depending on the type, but about 0.01 to about 10 parts by weight, preferably about 0.02 to about 5 parts by weight, based on 100 parts by weight of the monomer mixture may be used. In the above range, it may have excellent heat resistance, prevents the molecular weight of the polymer from being lowered too much and is excellent in mechanical properties.

In the production method of the (meth) acrylic copolymer of the present invention, a conventional suspension stability aid and the like can be further used together with the suspension stabilizer.

As the suspension stabilizer, organic suspension stabilizers such as polyalkyl acrylate-acrylic acid, polyolefin-maleic acid, polyvinyl alcohol, cellulose, and inorganic suspension stabilizers such as tricalcium phosphate may be used, but are not limited thereto.

As the suspension stability aid, disodium hydrogen phosphate, sodium dihydrogen phosphate, or the like may be used, and sodium sulfate or the like may be added to control solubility characteristics of the water-soluble polymer or monomer.

In the manufacturing method of the (meth) acrylic-type copolymer of this invention, the said polymerization temperature and polymerization time can be adjusted suitably. For example, it may be reacted for about 2 to about 8 hours at a polymerization temperature of about 65 to about 125 ° C, preferably about 70 to about 120 ° C.

After the polymerization is completed, it is possible to obtain a (meth) acrylic copolymer in the form of particles through cooling, washing, dehydration and drying.

The (meth) acrylic copolymer of the present invention may have a weight average molecular weight of about 5,000 to about 500,000 g / mol, preferably about 10,000 to about 250,000 g / mol, more preferably about 20,000 to about 200,000. It may have excellent impact resistance and flame resistance in the above range.

The (meth) acrylic copolymer may have a refractive index of about 1.510 to about 1.590, preferably about 1.520 to about 1.560 at a thickness of 2.5 mm, and a flame retardancy measured according to the UL94 evaluation method with a specimen of 3.2 mm, at least V2, eg For example, it may be V2 to V0.

In addition, the (meth) acrylic copolymer may have a total light transmittance of about 85% or more, preferably about 90% or more, measured in accordance with ASTM D1003 as a specimen having a thickness of 2.5 mm.

The thermoplastic resin according to the present invention comprises a polycarbonate resin and a resin containing a phosphorus-containing heterocyclic group, and in one embodiment, the thermoplastic resin is (A) a polycarbonate resin, and (B) the phosphorus-containing hetero It is characterized by including a (meth) acrylic copolymer containing a cyclic group.

In addition, the thermoplastic resin according to the present invention may further include (C) rubber-modified vinyl-based graft copolymer resin and / or (D) phosphorus-based flame retardant as necessary.

In the context of the present invention, "thermoplastic resin" means both the thermoplastic resin itself, as well as a blend of two or more thermoplastic resins and other additives (thermoplastic resin composition), and the like.

The polycarbonate resin (A) used in the present invention can be produced by reacting a dihydric phenol compound and a phosgene in the presence of a molecular weight modifier and a catalyst according to a conventional production method. In another embodiment, the polycarbonate resin (A) may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate.

In the production method of such a polycarbonate resin, a bisphenol compound may be used as the dihydric phenol compound, and preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used. . In this case, the bisphenol A may be partially or wholly replaced by another type of dihydric phenol compound. Examples of other types of dihydric phenolic compounds that can be used include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) cyclo Hexane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Halogenated bisphenols such as sulfoxide, bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether, and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane Can be mentioned.

However, the type of dihydric phenol compound that can be used for the production of the polycarbonate resin (A) is not limited thereto, and the polycarbonate resin may be manufactured using any dihydric phenol compound.

In addition, the polycarbonate resin (A) may be a homopolymer using one type of dihydric phenol compound, a copolymer using two or more types of dihydric phenol compounds, or a mixture thereof.

In general, the polycarbonate resin may have a form such as a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin. The polycarbonate resin (A) included in the thermoplastic resin of the present invention is not limited to a specific form, and any of these linear polycarbonate resins, branched polycarbonate resins, polyester carbonate copolymer resins, and the like can be used.

As said linear polycarbonate resin, bisphenol-A polycarbonate resin can be used, for example, As said branched polycarbonate resin, For example, polyfunctional aromatic compounds, such as trimellitic anhydride or trimellitic acid, May be prepared by reacting with a dihydric phenol compound and a carbonate precursor. As the polyester carbonate copolymer resin, for example, one produced by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor can be used. In addition, conventional linear polycarbonate resins, branched polycarbonate resins or polyestercarbonate copolymer resins can be used without limitation.

In the present invention, the polycarbonate resin (A) may be used alone or in combination of two or more kinds having different molecular weights.

The content of the polycarbonate resin (A) is about 50 to about 99% by weight, preferably about 55 to about 95% by weight of the resin containing (A) + (B), more preferably about 60 to about 90 wt%. It can have a good balance of mechanical properties and scratch resistance in the above range.

Further, in the thermoplastic resin of the present invention, the content of the (meth) acrylate copolymer (B) is about 1 to about 50% by weight, preferably about 5 to, of the resin containing (A) + (B). About 45% by weight, more preferably about 10 to about 40% by weight. In the above range, scratch resistance can be sufficiently improved, and impact and mechanical property deterioration can be prevented.

The rubber-modified vinyl graft copolymer (C) used in the present invention has a core-shell graft copolymer structure which is a structure in which an unsaturated monomer is grafted to a rubber core structure to form a shell, and thus impacts in a thermoplastic resin. It acts as an adjuvant.

As the rubber, it is preferable to use a polymer prepared by polymerizing one or more rubber monomers of a diene rubber, an acrylate rubber, and a silicone rubber having 4 to 6 carbon atoms, and in terms of structural stability, a silicone rubber is used alone. It is more preferable to use a silicone rubber and an acrylate rubber in combination.

As said acrylate type rubber, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (Meth) acrylate monomers, such as (meth) acrylate, can be used, At this time, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3- butylene glycol di (meth) acrylate And curing agents such as 1,4-butylene glycol di (meth) acrylate, allyl (meth) acrylate, and triallyl cyanurate.

The silicone rubber is prepared from cyclosiloxane, and specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenyl. It may be prepared from one or more selected from cyclotetrosiloxane, and octaphenylcyclotetrasiloxane. At this time, curing agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane and tetraethoxysilane can be further used.

The rubber may be included in about 50 to about 95 parts by weight, preferably about 60 to about 90 parts by weight, and more preferably about 70 to about 85 parts by weight of the rubber-modified vinyl graft copolymer (C). . It is excellent in compatibility with the resin in the above range, as a result can exhibit an excellent impact reinforcing effect.

The average particle diameter of the rubber may be about 0.1 to about 1 μm, preferably about 0.4 to about 0.9 μm. It may be more preferable to maintain the impact resistance and colorability balance in the above range.

Examples of the unsaturated monomer grafted to the rubber include at least one unsaturated compound of alkyl (meth) acrylate, (meth) acrylate, acid anhydride, and alkyl or phenyl nucleosubstituted maleimide having 1 to 12 carbon atoms. Can be used.

Specific examples of the alkyl (meth) acrylate may include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and the like, of which methyl methacrylate may be preferably used.

Carboxylic anhydrides, such as maleic anhydride and itaconic anhydride, can be used as said acid anhydride.

The grafted unsaturated monomer is about 5 to about 50 parts by weight, preferably about 10 to about 40 parts by weight, more preferably about 15 to about 30 parts by weight, in the rubber-modified vinyl-based graft copolymer (C). May be included as a wealth. It is excellent in compatibility with the resin in the above range, it can exhibit an excellent impact reinforcing effect.

The content of the rubber-modified vinyl graft copolymer resin (C) is about 0 to about 30 parts by weight, preferably about 3 to about 100 parts by weight of the base resin including the (A) + (B). About 20 parts by weight. In the above range, not only the impact reinforcing effect can be obtained, but also the mechanical strength such as tensile strength, flexural strength, flexural modulus, etc. can be improved.

Phosphorus-based flame retardant (D) used in the present invention is added to further secure flame retardancy, for example, phosphate (Phosphate), phosphonate (Phosphonate), phosphinate (Phosphinate), phosphine oxide ( Conventional phosphorus-containing flame retardants such as Phosphine Oxide, Phosphene and metal salts thereof can be used without limitation.

In one embodiment, as the phosphorus-based flame retardant (D) may be used that represented by the following formula (4).

[Formula 4]

In Formula 4, R ₉ , R ₁₀ , R _12, and R ₁₃ are each independently an aryl group having 6 to 20 carbon atoms, or a C 1 -C 10 alkyl substituted C 6 -C 20 aryl group, and R ₁₁ Is one derived from dialcohol of resorcinol, hydroquinol, bisphenol-A, or bisphenol-S, and p is an integer from 0 to 10.

In the above formula (4), i) p is specifically illustrated when 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) the case where p is 1 is concretely exemplified by resorcinol bis (diphenylphosphate). ), Hydroquinol bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis (2,6-dibutyl butylphenyl phosphate), hydroquinol bis (2,6-dimethylphenyl phosphate) There is this. iii) when p is 2 or more, is present in the form of a mixture in oligomeric form.

In another embodiment, the phosphorus-based flame retardant (D) may be used represented by the formula (5).

[Formula 5]

In Formula 5, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , and R ₂₃ each independently represent an alkyl group having 1 to 6 carbon atoms. , C 6 -C 20 aryl, C 1 -C 6 alkyl substituted C 6 -C 20 aryl, C 6 -C 20 aralkyl group, C 1 -C 6 alkoxy group, C 6 -C 20 aryloxy group, amino group or hydroxy group A substituent, R ₂₄ is a C6-C30 deoxyaryl group or a C6-C30 deoxyaryl group derivative substituted with an alkyl group, q is a number average polymerization degree, and the average value of q is 0.3 to 3, and k and j are It is an integer of 0-10. Herein, the alkoxy group or the aryloxy group of Formula 5 may be substituted with an alkyl group, an aryl group, an amino group, a hydroxyl group, or the like.

The phosphorous flame retardant (D) may be included in an amount of about 0 to about 20 parts by weight based on 100 parts by weight of the base resin including the (A) + (B), but is not limited thereto.

Thermoplastic resins according to the present invention, if necessary, flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, electrostatic Additives such as inhibitors, pigments, and dyes may be further included. The additives may be applied alone or by mixing two or more kinds. These additives may be added during the polymerization process of the (meth) acrylic copolymer (B), may be included in the (meth) acrylic copolymer (B) in the thermoplastic resin, and may be added to the usual pelletization process (extrusion process) of the thermoplastic resin. It may be included in the thermoplastic resin as a whole, but the method is not particularly limited. The additive may be included in an amount of about 0.001 to about 20 parts by weight based on 100 parts by weight of the resin (A) + (B), but is not limited thereto.

Non-limiting examples of such antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydrophenyl) propionate, triethylene glycol-bis-3 (3-tertary-butyl-4 -Hydroxy-5-methylphenyl) propionate, 2,6-di-tert-butyl-4-methyl phenol, 2,2'-methylenebis (4-methyl-6-tert-butylbutyl phenol), tri ( 2,4-di-tert-butylphenyl) phosphite, normal-octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, disterylthiol dipropio Nate, lauthiol propionate methane, di-phenyl-isooctyl propionate, and the like.

Thermoplastic resin of the present invention is a specimen having a thickness of 3.2mm, the flame retardancy measured according to UL94 may be V2 or more, for example, V2 to V0, and the scratch width according to the Balltype Scratch Profile Test. ) May be, for example, about 180 to about 350 μm, and pencil hardness may be in the range of 2B to 3H, for example.

The thermoplastic resin according to the present invention can be produced by a known thermoplastic resin manufacturing method. For example, the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder to produce pellets, and the pellets may be used to produce plastic injection and compression molded articles.

The (meth) acrylic copolymer and the thermoplastic resin according to the present invention may form a molded article. As a molding method for manufacturing the molded article, extrusion, injection, casting, etc. may be applied, but is not limited thereto. Such molding methods are well known to those skilled in the art. For example, the (meth) acrylic copolymer or the thermoplastic resin and, if necessary, the additives are mixed and then melt-extruded in an extruder to produce pellets, and the injection and compression molded articles are manufactured using the pellets. It can manufacture.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Example

Example 1

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 10% by weight, 15% by weight of allobiphenyl methacrylate monomer, 75% by weight of methyl methacrylate monomer 0.5 parts by weight of n-octyl mercaptan was mixed with respect to 100 parts by weight of the monomer mixture and the monomer mixture. In a stainless steel high pressure reactor equipped with a stirrer, 130 parts by weight of ion-exchanged water, 0.2 parts by weight of polyethylacrylate-methylacrylic acid (weight average molecular weight: 1 million or more), as a suspension stabilizer, based on 100 parts by weight of the monomer mixture. As a suspension aid stabilizer, a small amount such as disodium hydrogen phosphate and sodium sulfate was added and stirred. The monomer mixture containing n-octyl mercaptan was added to the aqueous solution in which the suspension stabilizer and the like were dissolved, followed by stirring, and the inside of the reactor was filled with an inert gas such as nitrogen, followed by 3 hours at 70 ° C and 2 hours at 110 ° C. After the polymerization, the reaction was terminated. After the reaction was terminated, the (meth) acrylic copolymer particles were obtained through washing, dehydration and drying. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Example 2

Instead of the monomer mixture of Example 1 above, 30% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 15% by weight of allobiphenyl methacrylate monomer, The above-described operation was carried out except that 0.3 parts by weight of n-octyl mercaptan was mixed with a monomer mixture comprising 52.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate monomer. (Meth) acrylic copolymer particles were obtained in the same manner as in Example 1. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Example 3

Instead of the monomer mixture of Example 1 above, 30% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 20% by weight of allobiphenyl methacrylate monomer, And a monomer mixture including 50% by weight of methyl methacrylate monomer, and 0.2 parts by weight of n-octyl mercaptan is mixed with respect to 100 parts by weight of the monomer mixture in the same manner as in Example 1 ( Meta) acrylic copolymer particles were obtained. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Example 4

Instead of the monomer mixture of Example 1 above, 5% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 20% by weight of parabiphenyl methacrylate monomer, The above-described operation was carried out using a monomer mixture comprising 72.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate monomer, and 0.5 parts by weight of n-octyl mercaptan was mixed based on 100 parts by weight of the monomer mixture. (Meth) acrylic copolymer particles were obtained in the same manner as in Example 1. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Example 5

Instead of the monomer mixture of Example 1 above, 30% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 15% by weight of parabiphenyl methacrylate monomer, The above operation was carried out except that 0.5 parts by weight of n-octyl mercaptan was mixed with a monomer mixture comprising 52.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate monomer. (Meth) acrylic copolymer particles were obtained in the same manner as in Example 1. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Example 6

Instead of the monomer mixture of Example 1 above, 30% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 15% by weight of parabiphenyl methacrylate monomer, And a monomer mixture comprising 55% by weight of methyl methacrylate monomer, and 0.3 parts by weight of n-octyl mercaptan is mixed with respect to 100 parts by weight of the monomer mixture in the same manner as in Example 1 above ( Meta) acrylic copolymer particles were obtained. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Example 7

Instead of the monomer mixture of Example 1, 20% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 15% by weight of allobiphenyl methacrylate monomer, 0.3 weight of n-octyl mercaptan, based on 100 weight parts of the monomer mixture, using a monomer mixture comprising 15 weight% of phenyl methacrylate monomer, 55 weight% of methyl methacrylate monomer, and 2.5 weight% of methyl acrylate monomer. (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1 except that the parts were mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 1.

Comparative Example 1

Instead of the monomer mixture of Example 1, using a monomer mixture comprising 97.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate monomer, and based on 100 parts by weight of the monomer mixture, n-octyl mercaptan 0.3 (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1 except that the parts by weight were mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.

Comparative Example 2

Instead of the monomer mixture of Example 1, using a monomer mixture comprising 20% by weight of the allobiphenyl methacrylate monomer, 77.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate monomer, and the monomer mixture 100 (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1, except that 0.3 parts by weight of n-octyl mercaptan was mixed with respect to parts by weight. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.

Comparative Example 3

Instead of the monomer mixture of Example 1, a monomer mixture comprising 20% by weight of parabiphenyl methacrylate monomer and 80% by weight of methyl methacrylate monomer was used, and based on 100 parts by weight of the monomer mixture, n- (Meta) acrylic copolymer particles were obtained in the same manner as in Example 1, except that 0.5 parts by weight of octyl mercaptan was mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.

Comparative Example 4

Instead of the monomer mixture of Example 1, using a monomer mixture comprising 30% by weight phenyl methacrylate monomer, 67.5% by weight methyl methacrylate monomer and 2.5% by weight methyl acrylate monomer, 100 parts by weight of the monomer mixture (Meth) acrylic copolymer particles were obtained in the same manner as in Example 1, except that 0.5 parts by weight of n-octyl mercaptan was mixed. Using the particles and the specimen extruded or injected, the physical properties were measured by the following physical property evaluation method, the results are shown in Table 2.

Specimen Manufacturing Method

100 parts by weight of the (meth) acrylic copolymer particles and 0.1 parts by weight of the hindered phenol-based heat stabilizer of Examples 1 to 7 and Comparative Examples 1 to 4 were added, followed by melting and kneading extrusion to prepare pellets. At this time, the extrusion was used a twin screw extruder having a diameter of L / D = 29, 45 mm, the prepared pellet was dried for 6 hours at 80 ℃, and injected into a 6 Oz injection machine to prepare a specimen.

Property evaluation method

(1) Weight average molecular weight (Mw): Measured by using GPC (Gel Permeation Chromatography) (unit: g / mol).

(2) Refractive index: It measured at 20 degreeC using the "DR-A1" refractor made by ATAGO company, and the thickness of the specimen was 2.5 mm.

(3) Flame retardant: A 3.2 mm thick specimen was prepared and flame retardant was measured by UL94 vertical test method. The results are shown in Table 1.

(4) Transparency: An injection molded product specimen having a thickness of 3.2 mm was prepared and evaluated by Haze (%) and total light transmittance (%) of the appearance of the injection molded product. In order to evaluate the transparency of the specimen, the total light transmittance (all transmitted light, TT) and Haze values were measured using a Nippon Denshoku Haze meter NDH 2000 instrument. The total transmitted light is the sum of the diffuse transmitted light (DF) and the parallel transmitted light (PT). The light quantity is calculated, and the Haze value is calculated by the following formula.

At this time, the higher the total transmitted light (TT), the lower the Haze is evaluated to be excellent in transparency.

Table 1 Example One 2 3 4 5 6 7 (a) 10 30 30 5 30 30 20 (b-1) 15 15 20 - - - 15 (b-2) - - - 20 15 15 - (c-1) 75 52.5 50 72.5 52.5 55 47.5 (c-2) - 2.5 - 2.5 2.5 - 2.5 (c-3) - - - - - - 15 Mw (× 1,000) 40 80 130 40 40 90 90 Refractive index 1.5238 1.5472 1.5550 1.5251 1.5472 1.5475 1.5476 Flame retardancy V2 V0 V0 V2 V0 V0 V1 Haze 1.1% 1.3% 1.6% 1.0% 1.2% 1.2% 1.3% Total light transmittance 92.0% 91.3% 91.2% 92.5% 92.6% 91.5% 91.4%

a: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, b-1: oxobiphenyl methacrylate monomer, b-2: parabiphenyl methacrylate Monomer, c-1: methyl methacrylate monomer, c-2: methyl acrylate monomer, c-3: phenyl methacrylate monomer

TABLE 2 Comparative example One 2 3 4 (a) - - - - (b-1) - 20 - - (b-2) - - 20 - (c-1) 97.5 77.5 80 67.5 (c-2) 2.5 2.5 - 2.5 (c-3) - - - 30 Mw (× 1,000) 80 80 40 50 Refractive index 1.4891 1.5192 1.5194 1.5134 Flame retardant Fail Fail Fail Fail Haze 1.3% 1.1% 1.2% 1.3% Total light transmittance 92.2% 92.0% 91.9% 92.1%

a: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, b-1: oxobiphenyl methacrylate monomer, b-2: parabiphenyl methacrylate Monomer, c-1: methyl methacrylate monomer, c-2: methyl acrylate monomer, c-3: phenyl methacrylate monomer

From the results of Tables 1 and 2, the (meth) acrylic copolymers (Examples 1 to 7) using the phosphorus-based (meth) acrylic monomers containing the phosphorus-containing heterocyclic group of the present invention are excellent in transparency and have a refractive index of 1.5238. It is higher than the above, it can be seen that the flame retardancy is excellent than V2. On the other hand, in Comparative Examples 1 to 4 without using the phosphorus (meth) acrylic monomer, the refractive index is 1.5194 or less, it can be seen that does not have a flame retardancy.

Hereinafter, the specifications of each component used in Examples and Comparative Examples are as follows:

(A) polycarbonate resin

PANLITE L-1250WP of TEIJIN, Japan, which is a bisphenol-A type linear polycarbonate resin, having a weight average molecular weight of 25,000 g / mol, was used.

(B) (meth) acrylic-type copolymer containing phosphorus containing heterocyclic group

(B1) (meth) acrylic copolymer-1 containing a phosphorus containing heterocyclic group

20% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 20% by weight of allobiphenyl methacrylate monomer, 60% by weight of methyl methacrylate monomer To prepare a copolymer by a conventional suspension polymerization method, the weight average molecular weight of the prepared copolymer was 85,000 g / mol.

(B2) (meth) acrylic copolymer-2 containing a phosphorus containing heterocyclic group

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer 10% by weight, parabiphenyl methacrylate monomer 15% by weight, methyl methacrylate monomer 75% by weight To prepare a copolymer by a conventional suspension polymerization method, the weight average molecular weight of the prepared copolymer was 40,000 g / mol.

(B3) (meth) acrylic copolymer-3 containing a phosphorus containing heterocyclic group

20% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxyl methacrylate monomer, 20% by weight of allobiphenyl methacrylate monomer, 37.5% by weight of methyl methacrylate monomer, phenyl The copolymer was prepared using a conventional suspension polymerization method using 20% by weight of methacrylate monomer and 2.5% by weight of methyl acrylate monomer, and the weight average molecular weight of the prepared copolymer was 125,000 g / mol.

(C) rubber-modified vinyl-based graft copolymer

METABLEN C-930A manufactured by Mitsubishi Rayon, Japan, in which a methyl methacrylate monomer was graft-polymerized in a butadiene / acrylic rubber composite, was used.

(D) phosphorus flame retardant

Resorcinolbis (diphenyl phosphate) was used.

(E) acrylic resin

L84 of LG MMA, a polymethyl methacrylate resin having a weight average molecular weight of 92,000 g / mol, was used.

(F) an acrylic copolymer having a refractive index of 1.513

30 wt% of the phenyl methacrylate monomer having a refractive index of 1.570 was prepared by a conventional suspension polymerization method using 70 wt% of methyl methacrylate monomer, and the weight average molecular weight of the prepared copolymer was 40,000 g / mol.

Examples 8-16 and Comparative Examples 5-12

After adding each of the components in the content as described in Tables 3 and 4, 0.1 parts by weight of a hindered phenol-based heat stabilizer was added, melted, kneaded and extruded to prepare a pellet. At this time, the extrusion was used a twin screw extruder having a diameter of L / D = 29, 45 mm, the prepared pellet was dried for 6 hours at 80 ℃, and injected into a 6 Oz injection machine to prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

Property measurement method

The transparency of the thermoplastic resin is evaluated by Haze of the appearance of the injection molded article and the total light transmittance (transmitted light), and the improved compatibility can be evaluated by the flow mark of the appearance.

(1) Flow mark: A specimen of size L90mm × W50mm × t2.5mm was prepared, and the presence or absence of a flow mark was visually observed. If there is no flow mark, it can be evaluated that the compatibility between the polycarbonate (A) and the (meth) acrylic copolymer (B) is improved.

(2) Transparency: The specimens were used to visually determine whether they were transparent, translucent, or opaque.

(3) Transparency: TT and Haze values were measured using a Nippon Denshoku's Haze meter NDH 2000 instrument. Combat overlight is calculated as the total amount of diffuse transmitted light (DF) and parallel transmitted light (PT). At this time, the higher the battle overlight (TT), the lower the Haze is evaluated to be excellent in transparency.

(4) Impact strength (Izod, unit: kgf · cm / cm): A notch was made in the 1/8 "Izod specimen by the evaluation method specified in ASTM D256 and evaluated.

(5) Heat resistance (VST, unit: ℃): measured under a load of 5kg weight, 50 ℃ / hr by the evaluation method specified in ASTM D1525.

(6) Flow index (MI) (unit: g / 10min): It measured on 250 degreeC and 2.16 kg conditions by the evaluation method prescribed | regulated to ASTMD1238.

(7) Flame retardant: A specimen having a thickness of 3.2 mm was prepared and flame retardant was measured by a UL94 vertical test method.

(8) Scratch resistance: measured by BSP (Ball-type Scratch Profile) test. Scratch lengths of 10 to 20 mm were applied to a L90 mm × W50 mm × t2.5 mm specimen surface using a 0.7 mm diameter spherical metal tip with a load of 1000 g and a scratch speed of 75 mm / min. Scratch width (µm), which is a measure of scratch resistance, was measured by surface scanning of the applied scratch using Ambios' contact surface profile analyzer (XP-1) with a metal stylus tip of 2 µm in diameter. At this time, the scratch resistance increases as the measured scratch width decreases.

(9) Pencil hardness: After leaving the specimen horizontal and vertical 100mm x 100mm at 23 ℃, 50% relative humidity for 48 hours, pencil hardness was measured according to JIS K 5401 standard. The scratch resistance is evaluated as 3B, 2B, B, HB, F, H, 2H, 3H, etc. according to the pencil hardness result. The higher the H value, the better the scratch resistance, and the higher the B value, the scratch resistance. This means that it is degraded.

TABLE 3 division Example 8 9 10 11 12 13 14 15 16 (A) 70 80 90 80 80 80 80 80 80 (B1) 30 20 10 - - - 20 - - (B2) - - - 20 20 - - 20 20 (B3) - - - - - 20 - - - (C) - - - - 5 5 - - 5 (D) - - - - - - 20 20 20 (E) - - - - - - - - - (F) - - - - - - - - - Flow mark radish radish radish radish radish radish radish radish radish Transparency Transparency Transparency Transparency Transparency Translucent Translucent Transparency Transparency Translucent Battle of Light (TT) 87.9 89.2 89.1 88.1 57.8 52.3 90.3 89.7 45.1 Izod impact strength 3.2 3.6 10.3 4.3 53.9 59.1 3.1 3.2 8.1 MI (g / 10 min) 33.1 15.3 10.1 21.4 10.3 4.3 23.3 26.1 18.0 Flame retardancy V2 V0 V0 V0 V1 V1 V0 V0 V0 Scratch resistance (㎛) 249 265 293 269 283 280 262 260 270 Pencil hardness H H HB F F F H H F

Table 4 division Comparative example 5 6 7 8 9 10 11 12 (A) 70 80 80 80 80 80 100 100 (B1) - - - - - - - - (B2) - - - - - - - - (B3) - - - - - - - - (C) - - 5 5 5 5 - 5 (D) - - - - 20 20 - 20 (E) 30 - 20 - 20 - - - (F) - 20 - 20 - 20 - - Flow mark U radish U radish U radish radish radish Transparency opacity Transparency opacity Translucent opacity Translucent Transparency Translucent Battle of Light (TT) 12.1 87.2 15.7 51.3 13.7 53.8 88.5 27.2 Izod impact strength 4.2 3.4 57.3 16.8 9.3 6.2 73.1 63.1 MI (g / 10 min) 6.1 17.1 4.0 14.8 14.9 33.0 6.3 23.1 Flame retardancy Fail Fail Fail Fail V0 V0 V2 V2 Scratch resistance (㎛) 253 267 279 285 274 276 332 307 Pencil hardness H F F F F F 2B HB

From the results of Tables 3 and 4, the thermoplastic resins (Examples 8 to 16) of the present invention have excellent impact strength and scratch resistance, and are compatible with (Flow mark), compared to the thermoplastic resins of Comparative Examples 5 to 12. It can be seen that transparency and transparency are excellent, and that flame retardancy is excellent at V2 or higher even without including a phosphorus-based flame retardant.

Simple modifications or changes of the present invention can be easily carried out 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 (19)

A (meth) acrylic copolymer containing a phosphorus containing heterocyclic group and a biphenyl group. The method according to claim 1, wherein the (meth) acrylic copolymer, (A) phosphorus-based (meth) acrylic monomers containing a phosphorus-containing heterocyclic group; (B) a biphenyl group-containing (meth) acrylic monomer having a refractive index of about 1.580 to about 1.700; And (C) It is a copolymer of the monomer mixture containing an unsaturated monomer, The (meth) acrylic-type copolymer characterized by the above-mentioned. The method according to claim 2, wherein the (meth) acrylic copolymer is about 1 to about 50 wt% of the phosphorus (meth) acrylic monomer (A), and about 1 to about 30 weight of the biphenyl group-containing (meth) acrylic monomer (B). % And about 20 to about 98 weight percent of said unsaturated monomer (C). The (meth) acrylic copolymer according to claim 2, wherein the phosphorus (meth) acrylic monomer (A) is represented by the following general formula (1): [Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrocarbon group of 1 to 20 carbon atoms, R ₃ and R ₄ are each independently a substituted or unsubstituted cyclic hydrocarbon group of 6 to 20 carbon atoms, m is an integer of 1-10, n is an integer of 0-5. The (meth) acrylic copolymer according to claim 2, wherein the biphenyl group-containing (meth) acrylic monomer (B) is represented by the following general formula (2): [Formula 2]

In Formula 2, R ₅ is a hydrogen atom or a methyl group, R ₆ is a substituted or unsubstituted biphenyl group or a substituted or unsubstituted terphenyl group, x is an integer of 0 to 10. The method of claim 2, wherein the unsaturated monomer (C) is an alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including (meth) acrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allyl glycidyl ether; Glycidyl methacrylate; And (meth) acrylic copolymers, characterized in that it comprises one or more of styrene monomers. 3. The (meth) acrylic copolymer according to claim 2, wherein the monomer mixture further comprises an alicyclic or aromatic (meth) acrylic monomer having a (D) refractive index of about 1.490 to about 1.579. The (meth) acrylic copolymer according to claim 7, wherein the alicyclic or aromatic (meth) acrylic monomer (D) is represented by the following general formula (3): [Formula 3]

In Formula 3, R ₇ is a hydrogen atom or a methyl group, R ₈ is a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X is an oxygen atom or Is a sulfur atom, y is an integer from 0 to 10, and Z is 0 or 1; 8. The (meth) acrylic copolymer according to claim 7, wherein the alicyclic or aromatic (meth) acrylic monomer (D) comprises about 0 to about 30% by weight of the total (meth) acrylic copolymer. 3. The (meth) acrylic copolymer according to claim 2, wherein the (meth) acrylic copolymer has a weight average molecular weight of about 5,000 to about 500,000 g / mol. The specimen of claim 1, wherein the (meth) acrylic copolymer has a refractive index of about 1.510 to about 1.590 at a thickness of 2.5 mm, a specimen having a thickness of 3.2 mm, a flame retardancy measured according to UL94 of V2 or more, and a specimen of 2.5 mm thickness. (Meth) acrylic copolymer, characterized in that the total light transmittance measured in accordance with ASTM D1003 is about 85% or more. The method of claim 2, wherein the (meth) acrylic copolymer is flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic material A (meth) acrylic copolymer further comprising at least one of an additive, an antistatic agent, a pigment and a dye. (A) polycarbonate resin; And (B) the (meth) acrylic copolymer according to any one of claims 1 to 12; Thermoplastic resin comprising a. The thermoplastic resin of claim 13, comprising about 50 to about 99 weight percent of the polycarbonate resin (A) and about 1 to about 50 weight percent of the (meth) acrylic copolymer (B). The thermoplastic resin according to claim 13, wherein the thermoplastic resin further comprises (C) a rubber-modified vinyl-based graft copolymer resin. The rubber-modified vinyl-based graft copolymer resin (C) has a structure in which a unsaturated monomer is grafted to a rubber core to form a shell, and the unsaturated monomer is an alkyl (meth) acryl having 1 to 12 carbon atoms. A thermoplastic resin comprising at least one of a rate, an acid anhydride, and an alkyl or phenyl-substituted maleimide having 1 to 12 carbon atoms. The thermoplastic resin according to claim 13, wherein the thermoplastic resin further comprises (D) phosphorus-based flame retardant. The method of claim 13, wherein the thermoplastic resin is flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additive, antistatic agent Thermoplastic resin further comprising at least one of pigments and dyes. The method of claim 13, wherein the thermoplastic resin has a thickness of 3.2 mm, the flame retardancy measured according to UL94 is V2 or more, and the scratch width according to the Balltype Scratch Profile Test is about 180 to The thermoplastic resin, characterized in that about 300 ㎛, pencil hardness is in the range of 2B to 3H.