KR20130073772A

KR20130073772A - Acrylic resin composition and articles comprising the same

Info

Publication number: KR20130073772A
Application number: KR1020110141788A
Authority: KR
Inventors: 정진화; 권기혜; 장주현; 구자관; 박광수
Original assignee: 제일모직주식회사
Priority date: 2011-12-23
Filing date: 2011-12-23
Publication date: 2013-07-03

Abstract

Acrylic resin composition excellent in impact resistance and scratch resistance of the present invention (A) Biphenyl group-containing (meth) acrylic copolymer 51 to 99% by weight; And (B) comprises 1 to 49% by weight of polycarbonate resin.

Description

Acrylic resin composition and its molded article {ACRYLIC RESIN COMPOSITION AND ARTICLES COMPRISING THE SAME}

The present invention relates to an acrylic resin composition and a molded article thereof. More specifically, the present invention provides an acrylic resin composition comprising a biphenyl group-containing (meth) acrylic copolymer and a polycarbonate resin and having excellent balance of physical properties such as excellent impact strength, scratch resistance, transparency, heat resistance, and appearance, and a molded article thereof. It is.

Thermoplastic resins have a lower specific gravity than glass or metal and have excellent physical properties such as excellent moldability and impact resistance. Recently, according 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 existing glass or metal areas, and are expanding the use area from electric and electronic products to automobile parts. As a result, the function of the exterior material and the performance of the appearance become important, and the demand for scratch resistance from external impacts and scratches is also increasing.

In particular, the polycarbonate resin is very excellent in mechanical strength and flame retardancy and excellent in transparency and weather resistance, but also excellent in impact resistance and thermal stability, but has a disadvantage in that scratch resistance is very weak.

Acrylic resins that can exhibit scratch resistance, in particular polymethyl methacrylate (PMMA) resins, are excellent in transparency and weather resistance, and have excellent mechanical strength, surface gloss, and adhesion, but have disadvantages of poor impact resistance and heat resistance. .

In order to overcome the above problems and simultaneously achieve physical properties including impact resistance and scratch resistance, a method of copolymerizing high refractive index monomers capable of exhibiting high refractive index and simultaneously exhibiting PMMA resins has been developed. . However, the copolymer in which the high refractive index monomers, which have been developed in the related art, have a limit in increasing the refractive index and the heat resistance.

Accordingly, the present inventors have developed an acrylic resin composition having excellent impact resistance and scratch resistance while maintaining transparency by adding a rubber modified vinyl graft copolymer to a biphenyl group-containing high refractive index acrylic resin and a polycarbonate blend in order to solve the conventional problems. Was done.

An object of the present invention is to provide an acrylic resin composition excellent in impact resistance and scratch resistance.

Another object of the present invention is to provide an acrylic resin composition having excellent heat resistance and impact resistance.

Still another object of the present invention is to provide an acrylic resin composition in which transparency is maintained during blending by applying an acrylic copolymer having high compatibility with polycarbonate.

Still another object of the present invention is to provide an acrylic resin composition in which a flow mark does not occur when a rubber-modified vinyl graft copolymer is applied.

Another object of the present invention is to provide a plastic molded article produced using the composition.

One aspect of the present invention relates to an acrylic resin composition. The acrylic resin composition comprises (A) 51 to 99% by weight of a biphenyl group-containing (meth) acrylic copolymer; And (B) comprises 1 to 49% by weight of polycarbonate resin.

In an embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) may include (A1) 1 to 50% by weight of a biphenyl group-containing (meth) acrylate having a refractive index of 1.580 to 1.700; (A2) 0 to 99% by weight monofunctional unsaturated monomer; And 0-50% by weight of a cycloaliphatic or aromatic (meth) acrylate having a refractive index of 1.490 to 1.579.

In embodiments, the biphenyl group-containing (meth) acrylate (A1) having a refractive index of 1.580 to 1.700 may include a structure represented by the following Chemical Formula 1.

[Formula 1]

(Wherein R1 is hydrogen or methyl group, m is an integer from 0 to 10, X is an allobiphenyl group, metabiphenyl group, parabiphenyl group, 2,6-terphenyl group, alloterphenyl group, metaterphenyl group and parater Phenyl group).

In embodiments, the alicyclic or aromatic (meth) acrylate (A3) having a refractive index of 1.490 to 1.579 may include a structure of Formula 2 or Formula 3.

[Formula 2]

(Wherein R1 is hydrogen or methyl group, m is an integer from 0 to 10, Y is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, propylphenyl group, cyclohexylphenyl group, chlorophenyl group, bromo Phenyl group and benzylphenyl group)

(3)

(Wherein R1 is hydrogen or methyl group, m is an integer from 0 to 10, Z is oxygen (O) or sulfur (S), Ar is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group , Cyclohexylphenyl group, chlorophenyl group, bromophenyl group and benzylphenyl group).

In embodiments, examples of the monofunctional unsaturated monomer (A2) include alkyl (meth) acrylates having 1 to 8 carbon atoms; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxy group; (Meth) acrylamide; Unsaturated nitrile; Allyl glycidyl ether; Glycidyl methacrylate; And styrene monomers, and these may be used alone or in combination of two or more thereof.

The biphenyl group-containing (meth) acrylic weight average molecular weight may be 3,000 to 300,000 g / mol.

In a specific embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) is characterized in that the non-crosslinked structure.

In a specific embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) has a glass transition temperature of 90 ° C. to 150 ° C., and may be extruded or injected at a temperature higher than the glass transition temperature.

In an embodiment, the acrylic resin composition may include (C) rubber-modified vinyl-based graft copolymer resin in an amount of greater than 0 to 30% by weight or less based on 100 parts by weight of the base resin including (A) + (B). do.

In a specific embodiment, 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. Anhydride, alkyl having 1 to 12 carbon atoms or phenyl nucleosubstituted maleimide, and the like, and the unsaturated monomer may be included alone or in combination of two or more.

In one embodiment, the acrylic resin composition 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 additives, colorants, It may further include additives such as stabilizers, lubricants, antistatic agents, pigments, dyes and flame retardants. The additives may be included alone or in combination of two or more.

Another aspect of the present invention relates to a molded article formed from the resin composition containing the acrylic resin composition. In embodiments, the molded article is 85% or more of combat over light, scratch resistance by the Ball-type Scratch Profile Test (width) is 210 μm or less width, heat resistance according to ASTM D1525 (load 5 kg, based on 50 ° C./hr).

In embodiments, the molded article has a warfare and light of at least 40%, scratch resistance by the Ball-type Scratch Profile Test (width) is less than 280 μm, heat resistance according to ASTM D1525 (load 5 Kg, 50 ° C./hr) may be 105 ° C. or higher and 1/8 ”Izod notch impact strength according to ASTM D256 of 8 kg · cm / cm or more.

Details of the present invention will be described in detail below.

The present invention relates to an acrylic resin composition having excellent impact and scratch resistance. The present invention relates to an acrylic resin composition having excellent properties such as transparency and scratch resistance of an acrylic resin, and at the same time showing improved impact resistance, thereby producing a plastic molded article exhibiting superior properties to existing products. It has the effect of the invention which can be preferably used in various electric and electronic parts or automobile parts.

Hereinafter, specific embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

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.

The acrylic resin composition comprises (A) 51 to 99% by weight of a biphenyl group-containing (meth) acrylic copolymer; And (B) 1 to 49% by weight of polycarbonate resin.

(A) Biphenyl group-containing (meth) acrylic copolymer

The biphenyl group-containing (meth) acrylic copolymer (A) used in the present invention includes (A1) 1 to 50% by weight of a biphenyl group-containing (meth) acrylate having a refractive index of 1.580 to 1.700; (A2) 0 to 99% by weight monofunctional unsaturated monomer; And (A3) 0 to 50% by weight of an alicyclic or aromatic (meth) acrylate having a refractive index of 1.490 to 1.579.

The biphenyl group-containing (meth) acrylate (A1) having the refractive index of 1.580 to 1.700 may include a structure represented by the following Chemical Formula 1.

[Formula 1]

(Wherein R1 is hydrogen or methyl group, m is an integer of 0 to 10, X is an allobiphenyl group, metabiphenyl group, parabiphenyl group, 2,6-terphenyl group, alloterphenyl group, metaterphenyl group, parater Selected from the group consisting of phenyl groups)

Examples of the biphenyl group-containing (meth) acrylate (A1) having a refractive index of 1.580 to 1.700 include allobiphenyl methacrylate, metabiphenyl methacrylate, parabiphenyl methacrylate, and 2,6-terphenyl methacrylate. Laterate, 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 necessarily limited thereto. These may be used alone or in combination of two or more.

Examples of the monofunctional unsaturated monomer (A2) are not particularly limited, and include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate; Acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Acid anhydrides such as unsaturated carboxylic acids such as acrylic acid and methacrylic acid, maleic anhydride and the like; Esters containing hydroxy groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; Acrylamide, methacrylamide, and the like, but are not necessarily limited thereto. These may be used alone or in combination of two or more.

The alicyclic or aromatic (meth) acrylate (A3) having the refractive index of 1.490 to 1.579 may include a structure of Formula 2 or Formula 3.

[Formula 2]

(3)

Examples of the alicyclic or aromatic (meth) acrylate (A3) having the refractive index of 1.490 to 1.579 include cyclohexyl methacrylate, phenoxy methacrylate, 2-ethylphenoxy methacrylate, benzyl methacrylate, and phenyl methacrylate. Acrylate, 2-ethylthiophenyl methacrylate, 2-phenylethyl methacrylate, 3-phenylporophyl 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 Late, 2- (4-chlorophenyl) ethyl methacrylate, 2- (4-bromophenyl) ethyl methacrylate , And the like, 2- (3-phenylphenyl) ethyl methacrylate, and 2- (4-benzylphenyl) ethyl methacrylate such as methacrylic acid and methacrylate, and these may be used alone or as a mixture of two or more.

The biphenyl group-containing (meth) acrylic copolymer (A) may be prepared by a conventional polymerization method, for example, bulk polymerization, emulsion polymerization or suspension polymerization. It may preferably be prepared by suspension polymerization.

In an embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) is a biphenyl group-containing (meth) acrylate monomer having a refractive index of at least 1.580 to 1.700 having the structure of Formula 1, and the monofunctional unsaturated monomer (B). And a monomer mixture containing an alicyclic or aromatic (meth) acrylate (A3) having at least one refractive index having a structure of Formula 2 or 3 of 1.490 to 1.579.

For example, a polymerization initiator and a chain transfer agent may be added to the monomer mixture to prepare a reaction mixture, and the reaction mixture may be prepared by suspension polymerization by adding a suspension stabilizer in an aqueous solution.

The polymerization temperature and the polymerization time can be appropriately adjusted. For example, the reaction may be performed for about 2 to 8 hours at a polymerization temperature of 65 to 125 ° C, preferably 70 to 120 ° C.

The polymerization initiator may use a conventional radical polymerization initiator known in the polymerization field. For example, the polymerization initiator may be octanoyl peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, tert-butyl perbenzo Polymerization initiators such as ate, azobisisobutyronitrile and azobis- (2,4-dimethyl) -valeronitrile may be used, but are not necessarily limited thereto. The polymerization initiator may be applied alone or by mixing two or more kinds. In an embodiment, the polymerization initiator may be included in an amount of 0.01 to 10 parts by weight, preferably 0.03 to 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 thermoplastic (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 mixture. 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 than the end of a chain having a double bond generated when a chain transfer agent is not used. Therefore, the addition of the chain transfer agent can improve the thermal stability, and eventually improve the optical properties of the thermoplastic (meth) acrylate copolymer.

The chain transfer agent may be a conventional chain transfer agent known in the polymerization art. For example, the chain transfer agent may comprise CH3 (CH2) including n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, isopropyl mercaptan, n-amyl mercaptan and the like. alkyl mercaptan in the form of nSH (n is an integer from 1 to 20); 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 necessarily limited thereto. These can be applied individually or in mixture of 2 or more types. The chain transfer agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer mixture. It may have thermal stability and an appropriate molecular weight in the above range. Preferably it is 0.02-5 weight part.

In an embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) may have a weight average molecular weight of 3,000 to 300,000 g / mol. Preferably, the weight average molecular weight of the biphenyl group-containing (meth) acrylic copolymer (A) may be 40,000 g / mol or more, for example, 50,000 to 250,000 g / mol. Within this range, compatibility and mechanical properties can be maintained at the same time.

In an embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) has a non-crosslinked structure, preferably a linear structure.

In a specific embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) has a glass transition temperature of 90 ° C to 150 ° C, preferably 101 ° C to 130 ° C. Extrusion or injection is possible at a temperature above the glass transition temperature.

In an embodiment, the biphenyl group-containing (meth) acrylic copolymer (A) may have a non-catalytic softening temperature (VST) of 100 to 140 ° C., measured at 5 kg load and 50 ° C./hr, according to ASTM D1525.

In addition, the biphenyl group-containing (meth) acrylic copolymer (A) has a refractive index of 1.495 to 1.640 at a thickness of 2.5mm, and a transmittance of 85% or more, measured according to ASTM D1003.

The biphenyl group-containing acrylic copolymer (A) is characterized in that the non-crosslinked structure. Preferably it has a linear structure. As such, the biphenyl group-containing (meth) acrylic copolymer (A) of the present invention is non-crosslinked and can be extruded and injected, and has excellent compatibility with other resins such as polycarbonate.

The biphenyl group-containing (meth) acrylic copolymer (A) is used in an amount of 51 to 99% by weight, preferably 55 to 90% by weight in the base resin containing (A) + (B). When used at less than 51% by weight is not enough to improve the scratch resistance, and when used at more than 99% by weight it is not preferable that the impact and mechanical properties are suddenly generated.

(B) Polycarbonate resin

The polycarbonate resin (B) may be prepared 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 may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate.

In the method for producing the polycarbonate resin (B), a bisphenol-based compound may be used as the dihydric phenol compound, preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Can be used. At this time, the bisphenol A may be partially or wholly replaced by other dihydric phenol compounds. Examples of other dihydric phenolic compounds that can be used include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Halogenated bisphenol such as bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) .

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

In addition, the polycarbonate resin (B) 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 (B) may take the form of a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin, and the like, and the polycarbonate resin included in the polycarbonate resin composition The linear polycarbonate resin, the branched polycarbonate resin, the polyester carbonate copolymer resin, or the like can be used without any particular limitation.

Among these, as said linear polycarbonate resin (B), a bisphenol-A polycarbonate resin can be used, for example, As said branched polycarbonate resin, For example, trimellitic anhydride, trimellitic acid, etc. What is produced by reacting a polyfunctional aromatic compound with a dihydric phenolic compound and a carbonate precursor can be used. As the polyester carbonate copolymer resin, for example, those prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor may be used. In addition, conventional linear polycarbonate resins, branched polycarbonate resins, or polyester carbonate copolymer resins can be used without limitation.

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

In the present invention, the polycarbonate resin (B) is used in 1 to 49% by weight of the base resin containing (A) + (B), preferably 10 to 40% by weight, more preferably 15 to 35% by weight % to be. If the polycarbonate resin is used in less than 1% by weight it is difficult to express the excellent mechanical properties of the polycarbonate, if it exceeds 50% by weight it is difficult to expect the scratch resistance of pencil hardness H or more. In addition, since the composition ratio is 10 to 99% by weight, which causes a significant decrease in transparency due to the decrease in compatibility when blending two kinds of resins, it aims to improve compatibility and scratch resistance at this weight ratio composition.

(C) rubber-modified vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer (C) used in the present invention has a structure in which a shell is formed by grafting an unsaturated monomer to a rubber core structure, and serves as an impact modifier in the resin composition.

The rubber is preferably prepared by polymerizing at least one rubber monomer selected from the group consisting of 4 to 6 carbon atoms, acrylate rubbers, and silicone rubbers, and using silicone rubber alone or silicone rubber and acryl. It is more preferable to use a rate-based rubber in combination because of its structural stability.

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 the group consisting of cyclotetrosiloxane, and octaphenylcyclotetrasiloxane. At this time, curing agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane and tetraethoxysilane can be further used.

The rubber is preferably included in 50 to 90 parts by weight, preferably 60 to 85 parts by weight with respect to 100 parts by weight of the core-shell graft copolymer according to the present invention. When the rubber is contained in 50 to 90 parts by weight, the compatibility with the resin is excellent, and as a result can exhibit an excellent impact reinforcing effect.

It is preferable that the average particle diameter of the said rubber is 0.1-1 micrometer. It is more preferable to maintain impact resistance and colorability in the above range.

Examples of the unsaturated monomer grafted to the rubber include one or more unsaturated compounds selected from the group consisting of alkyl (meth) acrylates having 1 to 12 carbon atoms, acid anhydrides, and alkyl or phenyl nucleosubstituted maleimides having 1 to 12 carbon atoms. Can be used.

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

Examples of the acid anhydride include carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride.

The grafted unsaturated monomer may be included in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 15 to 35 parts by weight, based on 100 parts by weight of the core-shell graft copolymer according to the present invention. . It is excellent in compatibility with the resin in the above range, as a result can exhibit an excellent impact reinforcing effect.

The rubber-modified vinyl graft copolymer (C) according to the present invention is 30 parts by weight or less based on 100 parts by weight of the base resin containing (A) a biphenyl group-containing (meth) acrylic copolymer and (B) a polycarbonate resin, For example, it is included in more than 0 to 30 parts by weight or less, preferably 3 to 20 parts by weight. When the content of the rubber-modified vinyl graft copolymer is included in an amount of 3 to 20 parts by weight, not only the impact reinforcing effect can be obtained, but also the mechanical strength such as tensile strength, flexural strength and flexural modulus can be improved.

The acrylic resin composition may be flame retardant, surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, thermal stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additive, colorant, stabilizer, lubricant, electrostatic Additives such as inhibitors, pigments, dyes and flame retardants can be used. These additives may be used alone or in admixture of two or more.

This invention provides the molded article which shape | molded the said resin composition. In one embodiment, the molded article is 85% or more of combat light, scratch resistance according to the Ball-type Scratch Profile Test is 210 μm or less in width, heat resistance according to ASTM D1525 (load 5 kg, based on 50 ° C./hr). For example, the molded article is 87% to 99% of combat light, scratch resistance by Ball-type Scratch Profile Test, width of 175-210 μm, heat resistance by ASTM D1525. (Load 5Kg, based on 50 ℃ / hr) may be 110 ~ 130 ℃.

In another embodiment, the molded article has at least 40% of combat light, scratch resistance of the Ball-type Scratch Profile Test of 280 μm or less, and heat resistance according to ASTM D1525. 5 Kg, 50 ° C./hr) may be 105 ° C. or higher and 1/8 ”Izod notch impact strength according to ASTM D256 of 8 kg · cm / cm or higher. For example, the molded article may have 45% to 70% of combat light. , Scratch-resistance by Ball-type Scratch Profile Test, 200 ~ 270 μm in width, heat resistance according to ASTM D1525 (load 5Kg, 50 ℃ / hr) based on 105 ~ 125 1/8 "Izod notch impact strength according to ° C and ASTM D256 may be 9-25 kg · cm / cm.

The composition of the present invention can be used in the molding of various products, in particular in electrical and electronic products, such as housings 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 provide a scope of protection as defined by the appended claims.

Example

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

(A) Biphenyl group-containing (meth) acrylic copolymer

(A1) biphenyl group-containing (meth) acrylic copolymer-1

A copolymer was prepared by a conventional suspension polymerization method using 82.5% by weight of methyl methacrylate monomer and 2.5% by weight of methyl acrylate in 15% by weight of an olsobiphenyl methacrylate monomer having a refractive index of 1.640. The weight average molecular weight was 55,000 g / mol and the refractive index was 1.5117.

(A2) Biphenyl group-containing (meth) acrylic copolymer-2

A copolymer was prepared by a conventional suspension polymerization method using 67.5% by weight of methyl methacrylate monomer and 2.5% by weight of acrylate in 30% by weight of an allobiphenyl methacrylate monomer having a refractive index of 1.640. The average molecular weight was 85,000 g / mol and the refractive index was 1.5343.

(A3) Biphenyl group-containing (meth) acrylic copolymer-3

A copolymer was prepared by a conventional suspension polymerization method using 85 wt% of methyl methacrylate monomer to 15 wt% of parabiphenyl methacrylate monomer having a refractive index of 1.640. The weight average molecular weight of the prepared copolymer was 100,000 g / mol and a refractive index of 1.5119.

(A4) Biphenyl group-containing (meth) acrylic copolymer-4

A copolymer was prepared by a conventional suspension polymerization method using 70 wt% of methyl methacrylate monomer and 15 wt% of phenyl methacrylate in 15 wt% of parabiphenyl methacrylate monomer having a refractive index of 1.640. The weight average molecular weight of was 100,000 g / mol and the refractive index was 1.5241.

(B) polycarbonate resin

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

(C) rubber-modified vinyl-based graft copolymer

METABLEN C-223A manufactured by Mitsubishi Rayon, Japan, where 20% by weight of styrene monomer and 10% by weight of methyl methacrylate monomer are graft polymerized in 70% by weight of butadiene rubber composite having an average particle diameter of 0.1 to 0.3 μm. Was used.

(E) acrylic resin

(E1) acrylic resin-1

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

(E2) acrylic resin-2

A copolymer was prepared by a conventional suspension polymerization method using 70 wt% of methyl methacrylate monomer to 30 wt% of phenyl methacrylate monomer having a refractive index of 1.570, and the weight average molecular weight of the prepared copolymer was 25,000 g / mol. .

(E3) acrylic resin-3

A copolymer was prepared by a conventional suspension polymerization method using 50 wt% of methyl methacrylate monomer to 50 wt% of phenyl methacrylate monomer having a refractive index of 1.570, and the weight average molecular weight of the prepared copolymer was 85,000 g / mol. .

Example 1 to 6 and Comparative example 1 to 7

Each component was added in an amount as described in Table 1 below, and then 0.1 part by weight of a hindered phenol-based heat stabilizer was added to melt, kneaded, and extruded pellets. At this time, 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 in a 6 Oz injection machine to prepare a specimen. Haze, impact strength, heat resistance, scratch resistance, and pencil hardness of the prepared specimens were measured by the following method. The measurement method is as follows. The results are shown in Tables 1 and 2 below.

How to measure

(1) Flow mark: It was visually observed using the specimen of L90mm x W50mm x t2.5mm, and evaluated as the presence or absence. Without the flow mark, the compatibility can be evaluated as improved.

(2) Transparency: Visual evaluation was carried out using specimens of L90mm × W50mm × t2.5mm.

(3) Battle light: The total transmitted light (TT) was measured using a Haze meter NDH 2000 instrument of Nippon Denshoku, and the total transmitted light was calculated as the total amount of diffuse transmitted light (DF) and parallel transmitted light (PT). At this time, the higher the total transmitted light (TT), the better the transparency.

(4) Impact Strength (Izod) (unit: kg · cm / cm): Notch was made in 1/8 "Izod specimens by evaluation method specified in ASTM D256.

(5) Scratch resistance (unit: micrometer): It measured by BSP (Ball-type Scratch Profile) test. The BSP test applied a scratch of 10 to 20 mm length with a load of 1000 g and a scratch speed of 75 mm / min using a 0.7 mm diameter spherical tip on a L90mm × W50mm × t2.5mm specimen surface. Scratch width is measured using Ambios' contact surface profile analyzer (XP-1) to measure scratch resistance by surface scan with a tip of a 2 μm diameter metal stylus. It was.

(6) Heat resistance (VST) (unit: degreeC): By the evaluation method prescribed | regulated to ASTM D1525, it measured on the load of 5Kg weight and 50 degreeC / hr conditions.

(7) Pencil hardness: After leaving the specimen at 23 ° C., 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. It means to be.

division Example Comparative example One 2 3 4 One 2 3 4 (A) Biphenyl group containing (meth) acrylic-type copolymer (A1) 70 - - - - - - - (A2) - 70 - - - - - - (A3) - - 70 - - - - 30 (A4) - - - 70 - - - - (A5) - - - - - - - - (B) PC 30 30 30 30 30 30 - 70 (E) acrylic resin (E1) - - - - 70 - 100 - (E2) - - - - - - - - (E3) - - - - - 70 - - Flow mark radish radish radish radish U radish radish radish transparency Transparency Transparency Transparency Transparency opacity Translucent Transparency Transparency Combat Lightning (TT) 90.5 89.3 90.2 88.7 5.8 72.1 91.3 88.2 Izod impact strength (1/8 ") 2.5 2.6 2.9 3.0 3.2 1.5 1.2 3.5 BSP Width (μm) 203 209 198 206 225 218 176 257 Heat resistance degree (VST) 112.5 112.7 114.2 111.1 110.3 109.0 105.2 125.7 Pencil hardness 2H 2H 2H 2H 2H 2H 3H H

As shown in Table 1, when mixing the conventional polymethyl methacrylate and polycarbonate as in Comparative Example 1, the flow mark occurs and an opaque milky appearance due to the decrease in compatibility between the two resins, which reduces the battle light You can check with In Comparative Example 2 using a high refractive index acrylic copolymer having a refractive index of 1.495 to 1.590 and a weight average molecular weight of 25,000 to 95,000, transparency and appearance were slightly improved compared to Comparative Example 1 using PMMA, but impact strength and heat resistance were improved. This was degraded and transparency and scratch resistance were not enough. It can be seen that Comparative Example 3, in which polymethyl methacrylate was applied alone without blending polycarbonate, significantly reduced the impact strength and the heat resistance. In addition, in the case of the comparative example 4 in which the ratio of a biphenyl group containing (meth) acrylic-type copolymer and polycarbonate resin was out of the range of this invention, it turns out that scratch resistance fell remarkably.

division Example Comparative example 5 6 5 6 7 (A) Biphenyl group containing (meth) acrylic-type copolymer- (A1) - - - - - (A2) - - - - - (A3) 70 - - - - (A4) - 70 - - - (A5) - - - - - (B) PC 30 30 30 30 - (C) Rubber modified vinyl graft copolymer 15 15 15 15 15 (E) acrylic resin (E1) - - 70 - 100 (E2) - - - 70 - (E3) - - - - - Flow mark radish radish U radish radish Transparency and Color opacity opacity opacity opacity opacity Combat Lightning (TT) 49.9 50.2 9.6 48.4 46.6 Izod impact strength (1/8 ") 12.0 10.9 17.6 5.9 5.5 BSP Width (μm) 253 263 257 250 242 Heat resistance degree (VST) 109.8 111.8 105.7 106.0 104.7 Pencil hardness H H H H H

As shown in Table 2, in Comparative Example 5 using the conventional PMMA resin can be confirmed by the flow mark generation and reduction of combat light. In Comparative Example 6 using a high refractive index acrylic copolymer having a weight average molecular weight of 25,000 to 95,000, transparency and appearance were slightly improved compared to Comparative Example 5 using PMMA, but impact strength and heat resistance were decreased. It wasn't enough. Comparative Example 7 without blending the polycarbonate can be seen that the impact strength and heat resistance is reduced.

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

(A) 51 to 99% by weight of a biphenyl group-containing (meth) acrylic copolymer; And
(B) 1 to 49% by weight of polycarbonate resin;
Acrylic resin composition comprising a.

The biphenyl group-containing (meth) acrylic copolymer (A) according to claim 1, wherein the biphenyl group-containing (meth) acrylic copolymer (A) has a refractive index of 1.580 to 1.700 (A1) of 1 to 50% by weight of a biphenyl group-containing (meth) acrylate; (A2) 0 to 99% by weight monofunctional unsaturated monomer; And 0-50% by weight of a cycloaliphatic or aromatic (meth) acrylate having a refractive index of 1.490 to 1.579. An acrylic resin composition containing a unit derived from a monomer comprising a.

The acrylic resin resin composition according to claim 2, wherein the biphenyl group-containing (meth) acrylate (A1) having a refractive index of 1.580 to 1.700 includes a structure represented by the following Chemical Formula 1.
[Formula 1]

The acrylic resin composition of claim 2, wherein the alicyclic or aromatic (meth) acrylate (A3) having a refractive index of 1.490 to 1.579 comprises a structure of Formula 2 or Formula 3 below:

(2)

(Wherein R1 is hydrogen or methyl group, m is an integer from 0 to 10, Y is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, propylphenyl group, cyclohexylphenyl group, chlorophenyl group, bromo Phenyl group and benzylphenyl group)

(3)

3. The monofunctional unsaturated monomer (A2) according to claim 2, wherein the monofunctional unsaturated monomer (A2) is an alkyl (meth) acrylate having 1 to 8 carbon atoms; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; (Meth) acrylate containing a hydroxyl group; (Meth) acrylamide; Unsaturated nitrile; Allyl glycidyl ether; Glycidyl methacrylate; And at least one selected from the group consisting of styrene monomers.

The acrylic resin composition according to claim 1, wherein the biphenyl group-containing (meth) acrylic copolymer (A) has a weight average molecular weight of 3,000 to 300,000 g / mol.

The acrylic resin composition according to claim 1, wherein the biphenyl group-containing (meth) acrylic copolymer (A) has a weight average molecular weight of 50,000 to 300,000 g / mol.

The acrylic resin composition according to claim 1, wherein the biphenyl group-containing (meth) acrylic copolymer (A) has a non-crosslinked structure.

The acrylic resin composition according to claim 1, wherein the biphenyl group-containing (meth) acrylic copolymer (A) has a glass transition temperature of 90 ° C to 150 ° C and is capable of extrusion or injection at a temperature above the glass transition temperature. .

The acrylic resin composition of claim 1, wherein the acrylic resin composition comprises (C) rubber-modified vinyl-based graft copolymer resin in an amount of greater than 0 to 30 parts by weight or less based on 100 parts by weight of the base resin including (A) + (B). Acrylic resin composition, characterized in that.

The rubber-modified vinyl-based graft copolymer resin (C) according to claim 10, wherein 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 alkyl (meth) acryl having 1 to 12 carbon atoms. Acrylic resin composition comprising at least one selected from the group consisting of a rate, an acid anhydride, alkyl having 1 to 12 carbon atoms or phenyl nucleosubstituted maleimide.

The method of claim 1, wherein the acrylic resin composition 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 additives, coloring agent And at least one selected from the group consisting of a stabilizer, a lubricant, an antistatic agent, a pigment, a dye and a flame retardant.

It is molded from the resin composition comprising the acrylic resin composition according to any one of claims 1 to 9 and 12, the combat light is at least 85%, to the Ball-type Scratch Profile Test (Ball-type Scratch Profile Test) Scratch resistance of the molded article characterized in that the width (width) is less than 210 μm, the heat resistance according to ASTM D1525 (load 5Kg, 50 ℃ / hr reference) is 110 ℃ or more.

It is molded from the resin composition comprising the acrylic resin composition according to any one of claims 10 to 11 and 12, the combat light is at least 40%, to the Ball-type Scratch Profile Test (Ball-type Scratch Profile Test) Scratch resistance by 280 μm or less width, heat resistance according to ASTM D1525 (load 5Kg, 50 ℃ / hr standard) is 105 ℃ or higher and 1/8 "Izod notch impact strength according to ASTM D256 8 kg Molded article characterized in that the cm / cm or more.