KR101134018B1 - Flame-Retardant Scratch-Resistant Thermoplastic Resin Composition with Improved Compatibility and Molded Article Using Thereof - Google Patents

Abstract

The flame retardant scratch resistant thermoplastic resin composition having improved compatibility of the present invention comprises (A) 40 to 80 parts by weight of a polycarbonate resin; (B) 1 to 50 parts by weight of modified (meth) acrylic copolymer resin; (C) 0.1-50 weight part of aromatic vinyl resin; 0.1-6 weight part of (D) fatty acid carboxylic acid amide compound with respect to 100 weight part of base resins containing said (A) + (B) + (C); (E) 1 to 50 parts by weight of a flame retardant; And (F) 1 to 30 parts by weight of the impact modifier.

Scratch resistance, flame retardancy, polycarbonate resin, modified (meth) acrylic resin, fatty acid carboxylic acid amide compound

Description

Flame-Retardant Scratch-Resistant Thermoplastic Resin Composition with Improved Compatibility and Molded Article Using Thereof}

Field of invention

The present invention relates to a flame retardant scratch-resistant thermoplastic resin composition and a molded article using the same having improved compatibility. More specifically, in the present invention, by applying a fatty acid carboxylic acid amide compound to a polycarbonate resin and a modified (meth) acrylic copolymer resin blend, not only flame retardancy but also surface impact strength and appearance are improved and compatibility without additional compatibilizer is improved. It relates to a flame-retardant scratch-resistant thermoplastic resin composition and a molded article using the same.

Background of the Invention

Thermoplastic resins have a lower specific gravity than glass or metal and have excellent moldability and impact resistance. With the recent trend of low cost, large size, and light weight of electric and electronic products, plastic products are rapidly replacing the existing glass or metal areas, thereby expanding the application area from electric and electronic products to automobile parts. In particular, LCD TVs are rapidly becoming larger in size, and as the design of TVs becomes a major selling point, the high gloss and color expression of plastic become more important. In addition, the scratch resistance of the resin is particularly required because the surface of the high-gloss surface is sharply degraded when a scratch occurs.

As the resin having good scratch resistance and gloss, an acrylic resin such as polymethyl methacrylate (hereinafter referred to as 'PMMA') is suitable, but it is difficult to secure desired flame retardancy with the acrylate resin itself. Accordingly, there is a problem that a resin composition containing PMMA resin as a main component is difficult to be used as an exterior material requiring excellent flame retardancy and impact strength.

Polycarbonate-based resins, on the other hand, have high heat resistance, impact strength and transparency, and are easily flame retardant, so that large heat dissipation such as automobile parts, monitors and TV housings or other office equipment requiring high mechanical strength and flame retardancy are required. Although applied to injection molding, there is a problem that scratch resistance is weak.

In general, a hard coat method of improving the scratch resistance of a resin surface by doping an organic-inorganic hybrid material on the surface of the final molded resin in order to improve the scratch resistance of the plastic, and then curing the surface with heat or ultraviolet rays. This is widely used. However, by the hard coating method, an additional process called a coating process is required, which takes a lot of time in the process, increases costs, and causes environmental problems. Therefore, as environmental issues and manufacturing cost issues are recently raised, a demand for an unpainted resin capable of expressing scratch resistance without hard coating is increasing. In addition, the development of a resin having excellent scratch resistance is very strongly demanded in the exterior material industry.

A method that can be approached to achieve scratch resistance and flame retardancy simultaneously while supplementing the above problems is to prepare a polycarbonate / polymethylmethacrylate blend (PC / PMMA) resin. However, there is a problem in that it is difficult to express high transparency and colorability due to a difference in refractive index and a decrease in compatibility between polycarbonate and acrylic resin. In addition, there is a disadvantage in that it is separated into each phase even when melt kneading at a high temperature due to such compatibility degradation. In particular, since the refractive index of PC is 1.59 and the refractive index of PMMA is 1.49, the alloy of PC and PMMA scatters light, making it difficult to color the color with high saturation. Therefore, it is very difficult to apply practically as an exterior material of an electric and electronic product.

In order to improve the compatibility of polycarbonate-based methacrylic resins, Korean Patent Publication No. 2004-0079118 discloses a method of lowering the molecular weight of polycarbonate during kneading by using a metal stearic acid ester. However, this method has the disadvantage that the mechanical properties are sharply lowered.

U. S. Patent No. 5,280, 070 uses a syndiotactic polymethylmethacrylate relative to polycarbonate to produce a transparent PC / PMMA blend but has the disadvantage of making it commercially difficult to produce syndiotactic polymethylmethacrylate resins.

Therefore, in order to solve the above problems, the present inventors apply a modified (meth) acrylic copolymer to a polycarbonate resin to reduce the refractive index difference between the resins and improve the compatibility between the polycarbonate and the acrylic resin, and at the same time, the fatty acid By introducing a carboxylic acid amide compound to further increase the compatibility with the resin to develop a flame-retardant scratch-resistant thermoplastic resin composition excellent in impact resistance and appearance.

An object of the present invention is to provide a flame-retardant scratch-resistant thermoplastic resin composition with improved compatibility.

Another object of the present invention is to provide a flame-retardant scratch-resistant thermoplastic resin composition that minimizes the decrease in colorability and improves the appearance by reducing the refractive index difference between the polycarbonate and the acrylic resin and improving compatibility.

Still another object of the present invention is to apply a fatty acid carboxylic acid amide compound to reduce frictional heat between polymer chains to facilitate processing, and to provide a flame retardant scratch-resistant thermoplastic resin composition which increases impact resistance by further increasing compatibility with a resin. will be.

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

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

Summary of the Invention

The present invention provides a flame retardant scratch resistant thermoplastic resin composition. The composition is (A) 40 to 80 parts by weight of a polycarbonate resin; (B) 1 to 50 parts by weight of modified (meth) acrylic copolymer resin; (C) 0.1-50 weight part of aromatic vinyl resin; 0.1-6 weight part of (D) fatty acid carboxylic acid amide compound with respect to 100 weight part of base resins containing said (A) + (B) + (C); (E) 1 to 50 parts by weight of a flame retardant; And (F) 1 to 30 parts by weight of the impact modifier.

In an embodiment, the modified (meth) acrylic copolymer resin (B) has a refractive index of 1.495 to 1.590.

The modified (meth) acrylic copolymer resin (B) may have a weight average molecular weight of 5,000 to 300,000.

In a specific example, the modified (meth) acrylic copolymer resin (B) is a polymer of (b1) 20 to 100% by weight of aromatic or aliphatic methacrylate and (b2) 0 to 80% by weight of monofunctional unsaturated monomer.

The monofunctional unsaturated monomers (b2) include methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxyl groups, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile. , Allyl glycidyl ether, glycidyl methacrylate, styrene monomers, and the like.

The aromatic vinyl resin (C) may be a polymer of 70 to 100% by weight of an aromatic vinyl compound and 0 to 30% by weight of a polymerizable unsaturated monomer.

In embodiments, the fatty acid carboxylic acid amide compound (D) may include an aliphatic carboxylic acid amide compound having 11 to 30 carbon atoms.

The flame retardant (E) may include one or more flame retardants selected from phosphorus flame retardants, halogen flame retardants and inorganic flame retardants.

The impact modifier (F) may be a copolymer obtained by graft polymerization of a vinyl monomer on a rubbery polymer.

The thermoplastic resin composition may be flame retardant, dropping, impact modifier, antioxidant, thermal stabilizer, light stabilizer, compatibilizer, pigment, dye, inorganic additive, antistatic agent, surfactant, nucleating agent, coupling agent. It may further include additives such as plasticizers, admixtures, lubricants, antibacterial agents, mold release agents, flame retardants.

Another aspect of the present invention provides a molded article molded from the resin composition. The molded article has a thickness of V-0 and a flame retardancy of 2.0 mm according to UL 94 V, and may have a surface impact strength of 3.0 mm thickness (1 m, 1 Kg) of 10 to 65 J.

Detailed Description of the Invention

(A) polycarbonate resin

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

[Formula 1]

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

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

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

In the present invention, the polycarbonate resin (A) is used in the range of 40 to 80 parts by weight. Since the polycarbonate resin has a role of facilitating flame retardancy, a problem of lowering flame retardancy and mechanical strength may occur when used below 40 parts by weight. have.

(B) Modified (meth) acrylic copolymer resin

The modified (meth) acrylic copolymer resin (B) of the present invention has a refractive index of 1.495 to 1.590. When the refractive index has the above range, it may have excellent compatibility when blended with the polycarbonate. In one embodiment, the modified (meth) acrylic copolymer resin (B) may have a refractive index of 1.51 to 1.59.

The modified (meth) acrylic copolymer resin (B) has a weight average molecular weight of 5,000 to 300,000. Excellent compatibility can be expressed in the above range. In embodiments, the weight average molecular weight may be 5,000 to 20,000. In other embodiments, the weight average molecular weight may be 30,000 to 100,000.

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

In a specific example, the modified (meth) acrylic copolymer resin (B) is a polymer of (b1) 20 to 100% by weight of aromatic or aliphatic methacrylate and (b2) 0 to 80% by weight of monofunctional unsaturated monomer. Preferably, the modified (meth) acrylic copolymer resin (B) is a polymer of 55 to 95% by weight of (b1) aromatic or aliphatic methacrylate and 5 to 45% by weight of (b2) monofunctional unsaturated monomer. In addition, the modified (meth) acrylic copolymer resin (B) may be a polymer of 25 to 45% by weight of (b1) aromatic or aliphatic methacrylate and 55 to 75% by weight of (b2) monofunctional unsaturated monomer. When aromatic or aliphatic methacrylate (b1) is used at 20 wt% or more, the average refractive index of the polymerized methacrylic copolymer resin can be maintained at 1.495 or more.

The (b1) aromatic or aliphatic methacrylate may be represented by the following formula (2) or (3).

[Formula 2]

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

(3)

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

Examples of the aromatic or aliphatic methacrylates include cyclohexyl methacrylate, phenoxy methacrylate, 2-ethylphenoxy methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethylthiophenyl methacrylate, 2-phenylethyl methacrylate, 3-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 Rate, 2- (4-bromophenyl) Methyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, and methacrylic acid, such as 2- (4-benzylphenyl) ethyl methacrylate, and the like. These may be used alone or in combination of two or more.

Examples of the monofunctional unsaturated monomer (b2) copolymerizable with the aromatic or aliphatic methacrylate (b1) include methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, acrylamides and meta Methamide, acrylonitrile, methacrylonitrile, allyl glycidyl ether, glycidyl methacrylate, styrene monomers and the like.

Specific examples include methacrylic acid esters including methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; Esters containing hydroxy groups, including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; Nitriles including acrylamide, methacrylamide, acrylonitrile and methacrylonitrile; Styrenic monomers including allyl glycidyl ether, glycidyl methacrylate, styrene and alphamethylstyrene, and the like, but are not necessarily limited thereto. These may be used alone or in combination of two or more.

In the present invention, when the modified (meth) acrylic copolymer resin (B) is blended with the polycarbonate resin, the modified (meth) acrylic copolymer resin is kneaded well with the polycarbonate due to the increased refractive index and improved compatibility of the modified (meth) acrylic copolymer resin. In addition, it is possible to reduce the transparency and coloring degradation caused by the difference in refractive index in the existing mixture. Therefore, it is possible to mix the polycarbonate and acrylic resin with improved compatibility and transparency, and it is possible to manufacture a high color and high transparency resin with improved scratch resistance of the existing polycarbonate.

In the present invention, the modified (meth) acrylic copolymer resin (B) is used in an amount of 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight, and most preferably 15 to 30 parts by weight. Can be. When the modified (meth) acrylic copolymer resin (B) is used in less than 1 part by weight, sufficient compatibility cannot be obtained, and when used in excess of 50 parts by weight, sufficient flame retardancy cannot be obtained.

(C) aromatic vinyl-based resin

The aromatic vinyl resin (C) of the present invention may be a polymer of an aromatic vinyl compound and a polymerizable unsaturated monomer.

In a specific example, the said aromatic vinyl resin (C) is a polymer of 70-100 weight% of aromatic vinyl compounds, and 0-30 weight% of polymerizable unsaturated monomers. In a specific embodiment, it may be a copolymer of 70 to 99% by weight of an aromatic vinyl compound and 1 to 30% by weight of a polymerizable unsaturated monomer.

The aromatic vinyl compound includes styrene, α-methylstyrene, halogen or alkyl substituted styrene, and the like, but is not limited thereto. These can be used individually or in mixture of 2 or more types, Preferably, they are styrene.

As the polymerizable unsaturated monomer, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl nucleosubstituted maleimide may be used. Preferred examples of the C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ acrylic acid alkyl esters are methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl. And at least one selected from esters, acrylonitrile and methacrylonitrile.

As the aromatic vinyl resin (C), an aromatic vinyl compound containing no rubber component may be used. Preferred examples of the aromatic vinyl resin (C) include polystyrene resin (GPPS) or styrene-vinyl cyanide copolymer resin (SAN). Most preferably of these are styrene-vinyl cyanide copolymer resins (SAN).

In embodiments, polymers of monomer mixtures of styrene and acrylonitrile and optionally methacrylic acid methyl ester; Polymers of acrylonitrile and optionally a mixture of monomers of methacrylic acid methyl ester; Or those prepared from monomer mixtures of styrene and α-methylstyrene with acrylonitrile and optionally methacrylic acid methylester.

The aromatic vinyl resin (C) may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and it is preferable to use a weight average molecular weight of 15,000 to 200,000. Preferably the weight average molecular weight is 50,000-170,000.

In the present invention, when the aromatic vinyl resin (C) is added to the blend of the polycarbonate resin and the modified (meth) acrylic copolymer resin, compatibility can be further improved. The aromatic vinyl-based resin (C) is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, most preferably 5 to 15 parts by weight of the total resin composition. When the aromatic vinyl resin (C) exceeds 50 parts by weight, scratch resistance may be deteriorated.

(D) fatty acid carboxylic acid amide compounds

The fatty acid carboxylic acid amide compound (D) of this invention contains a C11-30 aliphatic carboxylic acid amide compound. In other embodiments, the aliphatic carboxylic acid amide compound may comprise an unsaturated group.

In embodiments, the fatty acid carboxylic acid amide compound (D) may be represented by the following Chemical Formula 4 or Chemical Formula 5.

[Formula 4]

[Chemical Formula 5]

이고(l 및 n은 각각 6～20의 정수이고, m은 0 또는 1임), p는 1～5의 정수이다. 바람직하게는 l+n은 15～25이다. In the above, Q is

( L and n are each an integer of 6-20, m is 0 or 1), and p is an integer of 1-5. Preferably l + n is 15-25.

In one embodiment of Formula 4, m is 0 and l + n is 15-20. In another embodiment m may be 1, l may be 7-12, n may be 7-11. Preferred are steramid, oleamide, erucamide and the like. These can be used individually or in mixture of 2 or more types, Most preferably, they are steramid.

In one embodiment of Formula 5, m is 0, l + n is 15-20, and p is 1-3. Preferably, methylene bis stearamide or ethylene bis stearamide may be mentioned.

The fatty acid carboxylic acid amide compound (D) may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the base resin containing (A) + (B) + (C). Preferably it is 0.5-1 weight part. When the fatty acid carboxylic acid amide compound (D) is less than 0.1 part by weight, the compatibility is poor, the appearance is not good, and sufficient impact strength cannot be obtained. If it exceeds 6 parts by weight, flame retardancy may be lowered.

(E) flame retardant

As the flame retardant (E) of the present invention, a flame retardant commonly used may be used, and one or more selected from phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants may be used.

Preferred examples of the phosphorus-based flame retardant may include phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene, phosphazene, and metal salts thereof. It is not limited to this.

Aromatic phosphate ester compound or phosphate which is a representative compound of the phosphorus flame retardant may be representatively used a compound having a structure such as the formula (6);

[Formula 6]

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

In the aromatic phosphate ester compound, when i) n is 0, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trigylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, and tri (2) , 4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, and ii) when n is 1, resorcinolbis (diphenylphosphate), hydroquinolbis (diphenyl Phosphate), bisphenol A-bis (diphenylphosphate), resorcinolbis (2,6-dibutylbutylphenylphosphate), hydroquinolbis (2,6-dimethylphenylphosphate), and iii) n is 2; In the case more than may be present in the form of a mixture of oligomeric form. All or a mixture of two or more of the above-mentioned compounds are applicable.

The aromatic phosphate ester compound may be used alone or in a mixture with other phosphorus-containing flame retardants in the range of 0.5 to 40% by weight, preferably in the range of 5 to 40% by weight.

Examples of the halogen flame retardant include decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, octabromotrimethylphenyl indane, ethylene bistetrabromophthalimide, tris ( Tribromophenol) triazine, brominated polystyrene, etc. are mentioned, It is not necessarily limited to this. Particularly preferred is a halogen-based compound which can be melted at a normal processing temperature, more specifically a compound having a melting point or softening point at 250 ° C. or lower.

The inorganic flame retardant may be used well known in the art, it is easy to purchase commercially. Preferred examples include aluminum hydroxide, antimony oxide (trioxide, pentoxide), magnesium hydroxide, zinc stannate, molybdate or zirconium, more preferably antimony trioxide or antimony pentoxide, most preferably antimony trioxide May be used, but is not necessarily limited thereto.

The flame retardant (E) is 1 to 50 parts by weight, preferably 10 to 35 parts by weight, more preferably 15 to 1 part by weight based on 100 parts by weight of the base resin containing (A) + (B) + (C). It can be used in 30 parts by weight. When the flame retardant (E) is included in less than 1 part by weight, sufficient flame retardancy may not be obtained. If the flame retardant (E) is included in an amount greater than 50 parts by weight, physical properties such as impact strength or thermal stability may be degraded.

(F) impact modifier

As the impact modifier (F) of the present invention, a graft copolymer or an olefin copolymer can be used. In an embodiment, the copolymer is a graft polymerized vinyl monomer in a rubbery polymer. In a preferred embodiment, at least one selected from the group consisting of aromatic vinyl compound, unsaturated nitrile compound, C ₁ -C ₁₀ alkyl (meth) acrylate, maleic anhydride, alkyl and phenyl nucleosubstituted maleimide in 20 to 80% by weight of the rubbery polymer 20 to 90% by weight of the vinyl monomers are graft polymerized copolymers.

The rubbery polymer may be a diene rubber, an acrylate rubber, a silicone rubber, or an olefin rubber, but is not limited thereto.

Examples of the diene rubber include butadiene rubber or isoprene rubber. Preferred are polybutadiene, poly (styrene-butadiene) and the like. The acrylate rubber polymerizes monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacrylate. Can be used. The silicone rubber may be prepared from cyclosiloxane, and may be prepared from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotet Rosiloxane, octaphenylcyclotetrasiloxane, etc. are preferable. As the olefinic rubber, ethylene / propylene rubber, ethylene-propylene-diene terpolymer (EPDM), or the like may be used. These may be used alone or by mixing or copolymerizing two or more kinds.

The vinyl monomers include styrene, alpha-methyl styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate and butyl meth. It may be selected from the group consisting of acrylate, butyl acrylate, maleic anhydride, alkyl and phenyl nucleosubstituted maleimide.

The impact modifier (F) may be prepared by polymerizing the rubber monomer and then grafting a vinyl monomer capable of graft copolymerization to a rubbery polymer.

In one embodiment the impact modifier may have a core-shell structure. In another embodiment, the impact modifier may have a double core or double shell structure.

The impact modifier (F) is preferably applied in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin containing (A) + (B) + (C). If the impact modifier (F) exceeds 30 parts by weight, scratch resistance may be significantly reduced.

In the thermoplastic resin manufacturing method of the present invention, flame retardant, anti-dripping agent, impact enhancer, antioxidant, heat stabilizer, light stabilizer, compatibilizer, pigment, dye, inorganic additive, antistatic agent, surfactant, nucleating agent, Additives such as coupling agents, plasticizers, admixtures, lubricants, antibacterial agents, mold release agents, and flame retardants can be used. The additives may be applied alone or by mixing two or more kinds. The inorganic additives include glass fibers, silica, talc, ceramics, and the like, and their content is suitably 0 to 50 parts by weight based on 100 parts by weight of the base resin.

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

This invention provides the molded article which shape | molded the said resin composition. In one embodiment, the molded article may have a V-0 of 2.0 mm thick flame retardant by UL 94 V, and a 3.0 mm thick surface impact strength (1 m in height, 1 Kg) of 10 to 65 J.

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

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

Example

Specifications of each component used in the following 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) Modified (meth) acrylic copolymer resin

As the linear copolymer having a weight average molecular weight of 35,000, 70 parts by weight of methyl methacrylate and 30 parts by weight of phenyl methacrylate were copolymerized by suspension polymerization.

(B ') polymethyl methacrylate resin

Polymethyl methacrylate resin used as a comparative component was used LG IMA's IH830 Grade having a weight average molecular weight of 85,000.

(C) aromatic vinyl-based resin

SAN resin having an acrylonitrile content of 28.5 wt% and a weight average molecular weight of 125,000 was used.

(D) fatty acid carboxylic acid amide compounds

Ionchemistry HI-LUBE, a white bead type ethylene bis stearamide with a weight average molecular weight of 593, was used.

(D ') Modified Motanic Acid Wax

Montant wax of Clariant with a chain length of C ₂₈ -C ₃₂ was used.

(E) flame retardant

As bisphenol-A diphosphate, CR-741 manufactured by Daihachi Chemical Co., Ltd. was used.

(F) impact modifier

Mtable Metablen C223-A Grade was used.

Examples 1-4 and Comparative Examples 1-6

After adding each of the constituents in the content as shown in Table 1, 0.5 parts by weight of Teflon (trade name) Teflon (trade name) of Dupont, USA, was added as an antidropping agent and melt-kneaded at 220 to 260 ° C. in a conventional twin screw extruder to pellets. Prepared. The prepared pellets were dried at 80 ° C. for 3 hours and then injected at 8 ° C. in a molding temperature of 250 ° C. and mold temperature of 60 ° C. to prepare specimens and measured physical properties in the following manner.

(1) Impact strength: Izod impact strength was measured according to ASTM D-256 standard at 1/8 "thickness (kgf? Cm / cm).

(2) Surface impact strength: The surface impact was measured by dropping 1.0 KG weight from 1.0 m height using a DuPont Impact tester on a 10 × 10 cm 2, 3.0 mm thick specimen (J). ).

(3) Flame retardant: measured at 2.0 mm thickness according to UL 94 V flame retardant regulations.

(4) Appearance: The sharpness of the melt fusion line (joint surface formed by two flows in melt injection) or the flow mark was visually evaluated.

(5) Pencil hardness: It was measured in accordance with JIS K 5401 after leaving the specimen 10 × 10 cm 2 for 48 hours at 50% of 23 ° C relative humidity. Scratch resistance is evaluated as 3B, 2B, B, HB, F, H, 2H, 3H, etc. according to the pencil hardness results. The higher the H value, the better the scratch resistance.

As shown in Table 1, when the polycarbonate-based thermoplastic resin and the polymethyl methacrylate resin are blended (Comparative Example 3), the impact strength is high but the compatibility is not good, so the flow mark is clear and pearls according to the difference in refractive index The appearance of the pearl (Pearl) showed that the appearance performance is very degraded. When the polycarbonate-based thermoplastic resin and the modified acrylic copolymer resin were blended (Comparative Example 4), the appearance and the coloring were easy, but the impact strength was found to be low.

In the case of Examples 1, 2 and 3, the resin composition which showed the pencil hardness of H grade which is the outstanding scratch-resistance performance, and maintained the favorable external appearance which a flow mark is not seen was able to manufacture the resin composition which was remarkably excellent in impact resistance. In addition, the resins prepared in Examples 1, 2, and 3 had higher impact strength than the compositions (Comparative Examples 1, 2, 4) containing no fatty acid carboxylic acid amide compound (D), and had a weak surface impact strength. 2 times improved. Since the fatty acid carboxylic acid amide compound (D) reduces frictional heat between polymers, improves the flowability of the resin, facilitates processing, and increases compatibility with the resin, it can significantly increase impact resistance while maintaining scratch resistance. I could see that. Comparative Example 5 in which PMMA was applied instead of the modified (meth) acrylic copolymer resin was found to have a deteriorated appearance, and Comparative Example 6 in which a lubricant such as Modified Motanic Acid Wax was applied instead of the fatty acid carboxylic acid amide compound (D) had a surface impact. It can be seen that there is no increase effect.

The present invention has excellent appearance by reducing the refractive index difference between polycarbonate and acrylic resin and improving compatibility, including modified (meth) acrylic copolymer, and also adds fatty acid carboxylic acid amide compound to reduce frictional heat between polymer chains to process resin. And it has the effect of the invention to provide a thermoplastic resin composition excellent in impact resistance by increasing the compatibility with the resin.

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

Claims (12)

(A) 40-80 parts by weight of polycarbonate resin; (B) 1 to 50 parts by weight of modified (meth) acrylic copolymer resin; (C) 0.1-50 weight part of aromatic vinyl resin; Based on 100 parts by weight of the base resin containing the (A) + (B) + (C), (D) 0.1-6 weight part of fatty acid carboxylic acid amide compounds; (E) 1 to 50 parts by weight of a flame retardant; And (F) 1 to 30 parts by weight of the impact modifier; Wherein the modified (meth) acrylic copolymer resin (B) comprises (b1) 20 to 100% by weight of an aromatic or aliphatic methacrylate having a structure of Formula 2 or Formula 3 and (b2) a monofunctional unsaturated monomer: A flame retardant scratch-resistant thermoplastic resin composition, characterized in that the polymer is from to 80% by weight of: [Formula 2]

Wherein m is an integer of 0 to 10, X is a cyclohexyl group, a phenyl group, a methylphenyl group, a methylethylphenyl group, a propylphenyl group, a methoxyphenyl group, a cyclohexylphenyl group, a chlorophenyl group, a bromophenyl group, a phenylphenyl group and a benzylphenyl group Selected from the group consisting of (3)

(Wherein m is an integer of 0 to 10, Y is oxygen (O) or sulfur (S), Ar is cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group , Bromophenyl group, phenylphenyl group and benzylphenyl group). The flame retardant scratch-resistant thermoplastic resin composition of claim 1, wherein the modified (meth) acrylic copolymer resin (B) has a refractive index of 1.495 to 1.590. The flame-retardant scratch-resistant thermoplastic resin composition of claim 1, wherein the modified (meth) acrylic copolymer resin (B) has a weight average molecular weight of 5,000 to 300,000. delete The method of claim 1, wherein the monofunctional unsaturated monomer (b2) is methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid esters including rate; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; Esters containing hydroxy groups, including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; Nitriles including acrylamide, methacrylamide, acrylonitrile and methacrylonitrile; An improved flame retardant scratch-resistant thermoplastic resin composition, characterized in that at least one selected from the group consisting of styrenic monomers including allyl glycidyl ether, glycidyl methacrylate, styrene and alphamethylstyrene. The method of claim 1, wherein the aromatic vinyl resin (C) is 70 to 100% by weight of an aromatic vinyl compound, acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ Highly compatible flame-retardant scratch-resistant thermoplastic resin, characterized in that the polymer is 0-30% by weight of a polymerizable unsaturated monomer selected from the group consisting of acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl nucleosubstituted maleimide Composition. The composition of claim 1, wherein the fatty acid carboxylic acid amide compound (D) is represented by the following general formula (4) or (5). [Formula 4]

[Chemical Formula 5]

In the above, Q is

( L and n are each an integer of 6-20, m is 0 or 1), and p is an integer of 1-5. The flame-retardant thermoplastic resin composition of claim 1, wherein the flame retardant (E) comprises at least one flame retardant selected from phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants. The impact modifier (F) according to claim 1, wherein the impact modifier (F) is used in an aromatic vinyl compound, unsaturated nitrile compound, C ₁ -C ₁₀ alkyl (meth) acrylate, maleic anhydride, alkyl and phenyl nucleosubstituted maleic acid in 20 to 80% by weight of the rubbery polymer. Flame retardant scratch-resistant thermoplastic resin composition, characterized in that 20 to 80% by weight of at least one vinyl monomer selected from the group consisting of meads is a graft polymerized copolymer. The method of claim 1, wherein the thermoplastic resin composition is flame retardant, anti-dropping agent, impact modifier, antioxidant, heat stabilizer, light stabilizer, compatibilizer, pigment, dye, inorganic additive, antistatic agent, surfactant, nucleating agent, coupling agent, Flame-retardant scratch-resistant thermoplastic resin composition further comprises an additive selected from the group consisting of plasticizers, admixtures, lubricants, antibacterial agents, mold release agents, flame retardants and mixtures thereof. The molded article molded from the resin composition of any one of Claims 1-3 and 5-10. The molded article according to claim 11, wherein the molded article has a 2.0 mm thickness flame retardancy of V-0 according to UL 94 V, and a 3.0 mm thick surface impact strength (1 m in height, 1 Kg) of 10 to 65 J.