KR100817563B1 - Scratch-resistant flameproof thermoplastic resin composition - Google Patents

Abstract

A scratch-resistant flameproof thermoplastic resin composition is provided to be superior in both scratch resistance and flame retardancy, have excellent scratch resistance, and exhibit primary colors such as high black. A scratch-resistant flameproof thermoplastic resin composition includes (A) 100 parts by weight of a base resin, (B) 1-30 parts by weight of a phosphorous-based compound, and (C) 1-30 parts by weight of a halogen-based compound. The base resin comprises (a1) 20-80wt% of a polycarbonate-based resin and (a2) 20-80wt% of an alkyl(meth)acrylate-based resin. The resin composition further comprises (D) 1-30 parts by weight of an impact reinforcing agent based on 100 parts by weight of the base resin.

Description

Scratch-Resistant Flameproof Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition excellent in scratch resistance. More specifically, the present invention is a thermoplastic resin having excellent scratch resistance as well as flame resistance by applying a mixture of a phosphorus compound and a halogen compound to a base resin in which a polycarbonate resin and an alkyl (meth) acrylate resin are mixed in an appropriate ratio. It relates to a resin composition.

Background of the Invention

Recently, according to the trend of larger, specialized, and lighter electric appliances, various characteristics of resins are required. In particular, as the appearance of the exterior material is more important, scratch resistance of the resin is required, and flame retardancy is also required due to safety issues against fire.

In general, polycarbonate resin has been very popular as a resin excellent in mechanical strength and excellent in transparency, thermal stability, self-extinguishability, dimensional stability, etc., and is particularly widely used in electrical and electronic products and automotive parts. Polycarbonate resin is easy to achieve flame retardancy with a conventional flame retardant, but the scratch resistance of the polycarbonate itself is not good in and out of the pencil hardness B, there is a problem that can not achieve good scratch resistance with only polycarbonate resin.

On the other hand, in the case of alkyl (meth) acrylate-based resin such as polymethyl methacrylate (PMMA) resin, the pencil hardness of the resin itself is excellent scratch resistance of about 2H, but has a disadvantage that is difficult to achieve flame retardancy with conventional flame retardant have.

When blending an alkyl (meth) acrylate-based resin such as PMMA resin to supplement the scratch resistance of the polycarbonate resin, there is a problem that it is difficult to achieve flame retardancy due to the flame retardancy of the PMMA resin. In particular, since PMMA does not have a char generation capability, it is impossible to achieve flame retardancy by applying a phosphate-based flame retardant, and when a halogen-based flame retardant is applied, a large amount of PMMA is required due to the decomposition characteristics of PMMA itself. Have

Therefore, in order to solve the above problems, the present inventors apply a mixture of a phosphorus compound and a halogen compound to a base resin mixed with a polycarbonate resin and an alkyl (meth) acrylate resin at an appropriate ratio, thereby simultaneously providing scratch resistance and flame resistance. It is early to develop a resin composition which can be secured.

An object of the present invention is to provide a thermoplastic resin composition excellent in scratch resistance and flame retardancy at the same time.

Another object of the present invention is to provide a scratch-resistant flame retardant thermoplastic resin composition excellent in impact strength.

Still another object of the present invention is to provide a scratch-resistant flame retardant thermoplastic resin composition capable of expressing primary colors such as high black.

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

Hereinafter, the content of the present invention will be described in detail below.

Summary of the Invention

The scratch-resistant flame-retardant thermoplastic resin composition of the present invention (A) (a ₁ ) 20 to 80% by weight of a polycarbonate resin; And (a ₂ ) 100 parts by weight of a base resin composed of 20 to 80 wt% of an alkyl (meth) acrylate resin; (B) 1 to 30 parts by weight of the phosphorus compound; And (C) comprises 1 to 30 parts by weight of a halogen-based compound.

The phosphorus-based compound is a group consisting of phosphorus (Phosphate), phosphonate (Phosphonate), phosphinate (Phosphinate), phosphine oxide (Phosphine Oxide), phosphazene (metal), and salts thereof Can be selected from.

In one embodiment of the present invention, the phosphorus compound is an aromatic phosphate ester compound.

In the present invention, the halogen-based compound is composed of decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, tribromophenol triazine, brominated polystyrene and mixtures thereof It can be selected from the group.

In another embodiment of the present invention, the resin composition may further include 1 to 30 parts by weight of the impact modifier based on 100 parts by weight of the base resin.

In another embodiment of the invention the impact modifier is a rubber modified graft copolymer.

The rubber-modified graft copolymer is styrene, alpha-methyl styrene, alkyl substituted styrene to a rubbery polymer polymerized with at least one rubber monomer selected from the group consisting of diene rubber, acrylate rubber, and silicone rubber monomer; Acrylonitrile, methacrylonitrile; Methyl methacrylate; Maleic anhydride; It is produced by graft polymerization of a monomer selected from the group consisting of alkyl or phenyl nucleosubstituted maleimide and mixtures thereof.

In a specific embodiment of the present invention, the rubber modified graft copolymer is a resin (MBS resin) prepared by graft copolymerization of methyl methacrylate and styrene on butadiene rubber.

The resin composition of the present invention may further include an additive selected from the group consisting of anti-dripping agents, antioxidants, plasticizers, thermal stabilizers, light stabilizers, compatibilizers, pigments, dyes, inorganic additives and mixtures thereof.

The present invention provides pellets obtained by extruding the resin composition.

Detailed Description of the Invention

The flame retardant thermoplastic resin composition excellent in scratch resistance according to the present invention comprises a polycarbonate resin, an alkyl (meth) acrylate resin, a phosphorus compound and a halogen compound. Hereinafter, each component of this invention is demonstrated in detail below.

(A) Basic resin

(a ₁ ) polycarbonate resin

The aromatic polycarbonate resin (a ₁ ) according to the present invention may be prepared by reacting diphenols represented by the following formula ( ₁ ) with phosgene, halogen formate or carbonic acid diester.

[Formula 1]

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

Specific examples of the diphenol of Formula 1 include hydroquinol, resorcinol, 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 about 10,000 to 200,000, preferably about 15,000 to 80,000.

The polycarbonate resin of the present invention may be used having a branched chain. Preferably it can be prepared by adding about 0.05-2 mol% of tri- or more polyfunctional compounds, such as compounds having trivalent or more phenol groups, relative to the total amount of diphenols used for the polymerization.

In the present invention, the polycarbonate resin (a ₁ ) is used in the range of 20 to 80% by weight based on 100 parts by weight of the base resin. In the present invention, since the polycarbonate resin plays a role of facilitating flame retardancy, when applied at less than 20% by weight, flame retardancy and mechanical strength decrease, and when applied in excess of 80% by weight, the scratch resistance is expected to be improved. It is difficult to do

(a ₂ ) Alkyl (meth) acrylate resin

Alkyl (meth) acrylate resins used in the present invention include methyl acrylate resin, ethyl acrylate resin, propyl acrylate resin, butyl acrylate resin, alkyl acrylate resin such as 2-ethylhexyl acrylate resin, poly Alkyl methacrylate resins such as methyl methacrylate (PMMA) resin, ethyl methacrylate resin, propyl methacrylate resin, butyl methacrylate resin and mixtures thereof.

Among them, polymethyl methacrylate (PMMA) resin is most preferred for the scratch resistance improvement effect.

In the present invention, the alkyl (meth) acrylate resin is 20 to 80% by weight based on 100 parts by weight of the base resin. If it is less than 20% by weight it is difficult to impart scratch resistance and when applied in excess of 80% by weight, the flame retardancy is very low. In particular, it is difficult to achieve flame retardancy with a phosphorus-containing flame retardant.

(B) phosphorus compounds

Phosphorus-based compound in the present invention has a small flame retardant effect on the alkyl (meth) acrylate-based resin, but serves to give plasticity to facilitate processing.

The phosphorus compound refers to a common phosphorus-containing flame retardant, phosphate (Phosphate), phosphonate (Phosphonate), phosphinate (Phosphinate), phosphine oxide (Phosphine Oxide), phosphazene And metal salts thereof may be applied.

Preferably, it is an aromatic phosphate ester compound (Phosphate) represented by following General formula (2).

[Formula 2]

(In the above formula, R _1, R _2, R _4, R ₅ may be independently applied to each other as an aryl group or alkyl-substituted aryl group of C ₆ ~ C ₂₀ , R ₃ is resorcinol, hydroquinol, bisphenol- One of those derived from dialcohols such as A and bisphenol-S, and n has a value of 0 to 5).

The aromatic phosphate ester compounds may be used alone or in mixture with other phosphorus-containing flame retardants.

In the present invention, the phosphorus compound is used in an amount of about 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the base resin. When using less than 1 part by weight, the flame retardant effect is inferior, and when it exceeds 30 parts by weight, there is a problem of promoting the decomposition of the alkyl (meth) acrylate-based resin to reduce scratch resistance.

(C) halogen-based compound

In the present invention, the halogen-based compound is used as a flame retardant, and commercially available halogen-based compounds may be used. Applicable halogen compounds include commercially available flame retardants such as decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, tris (tribromophenyl) triazine and brominated polystyrene. It is possible to apply.

Particular preference is given to halogen-based compounds which are capable of melting at normal processing temperatures, more particularly compounds having a melting point or softening point at or below about 250 ° C.

In the present invention, the halogen-based compound may be used in the range of about 1 to 30 parts by weight with respect to 100 parts by weight of the base resin, preferably 10 to 25 parts by weight. When using less than 1 part by weight, the flame retardant effect is inferior, and when used in excess of 30 parts by weight, it may promote the decomposition of the alkyl (meth) acrylate-based resin to reduce the scratch resistance.

In the present invention, no antimony compound is added. Antimony compounds, such as antimony trioxide, are known to be synergistic in their flame retardancy when used in combination with halogen compounds, and are essential additives for the production of flame retardant resins using halogen flame retardants. However, since the antimony compound has a high refractive index, it serves as a white pigment for the final resin. Therefore, when using an antimony compound, since it is difficult to express primary colors, such as high black, an antimony compound is excluded from this invention.

(D) impact modifier

In the present invention, the impact modifier may be optionally added, and a rubber-modified graft copolymer or an olefin copolymer may be used.

The rubber-modified graft copolymer is styrene, alpha-methyl styrene, alkyl substituted styrene capable of graft copolymerization to a rubbery polymer; Acrylonitrile, methacrylonitrile; Methyl methacrylate; Maleic anhydride; It is produced by grafting a monomer of one species selected from the group consisting of alkyl or phenyl nucleosubstituted maleimide. The rubber content of the rubber-modified graft copolymer is preferably 20 to 80% by weight.

The rubbery polymer is obtained by polymerizing at least one rubber monomer selected from the group consisting of diene rubber, acrylate rubber, and silicone rubber monomer.

Butadiene is typically used as a monomer as the diene rubber, and isoprene may be applied. As the acrylate rubber, monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacrylate are used. do. The silicone rubber may be prepared from cyclosiloxane, and examples of cyclosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, Tetramethyltetraphenylcyclotetrosiloxane, octaphenylcyclotetrasiloxane, and the like. Silicone rubber can be used by selecting 1 or more types from the said cyclosiloxane. In addition, polyolefin type rubbers, such as ethylene / propylene rubber and ethylene-propylene-diene terpolymer (EPDM), can be used.

Impact reinforcing agent used in the present invention can be selectively applied according to the use, it is preferred to apply about 1 to 30 parts by weight based on 100 parts by weight of the base resin. When used in less than 1 part by weight, the impact reinforcing effect is inferior, and when used in excess of 30 parts by weight, the compatibility with the resin is lowered, scratch resistance and flame retardancy is reduced.

In the thermoplastic resin manufacturing method of the present invention, an antidrip agent such as polytetrafluoroethylene, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a pigment, a dye, an inorganic additive, or a mixture thereof may be added according to each use. Can be.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

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 to illustrate 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) Basic resin

(a ₁ ) polycarbonate resin

Panlite L-1225 Grade from Teijin, Japan, was used.

(a ₂ ) Alkyl (meth) acrylate resin

Cheil Industries' polymethyl methacrylate resin (PMMA) TP-100 was used.

(B) phosphorus compounds

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

(C) halogen-based compound (FR-245)

FR-245 from DEAD SEA BROMINE COMPANY, with a bromine content of 67%, was used as tris (tribromophenyl) triazine.

(D) Impact modifier (MBS: Methymethacrylate-Butadiene-Styrene)

As a resin (MBS resin) graft copolymerized with methyl methacrylate and styrene in butadiene rubber, Mtable Metablen C223-A Grade was used.

(E) anti-dripping agent (PTFE: Polytetrafluoroethylene)

Teflon (trade name) 7AJ of Dupont, USA was used.

Example  1 to 2

Each component was added to the content shown in Table 1 below and extruded at a temperature range of 220 ~ 260 ℃ in a conventional twin screw extruder to prepare a pellet. 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 impact, flame retardant, and pencil hardness specimens.

Comparative Examples 1 to 4

Comparative Examples 1 and 2 were carried out in the same manner as in Example 1, except that the phosphorus compound or the halogen compound was applied alone.

In Comparative Example 3, in the base resin, the ratio of PMMA resin was used beyond the scope of the present invention.

In Comparative Example 4, in the basic resin, the proportion of the PC resin was used beyond the scope of the present invention.

Physical properties of the specimens prepared by the above Examples and Comparative Examples were evaluated according to the following methods.

(1) Flame retardant: Flame retardancy was measured according to UL 94 V flame retardant at 2.5 mm thickness.

(2) Izod impact strength: measured in accordance with ASTM D-256 specification at 1/8 "thickness (kgfcm / cm).

(3) Pencil hardness: After leaving for 48 hours at 23 ℃ relative humidity 50% for 10 × 10 cm 2 specimens, the 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. The higher the B value, the lower the scratch property. Means that. The experimental results are shown in Table 1.

As shown in Table 1, Example 1-2 was confirmed to show the V0 flame retardancy of the highest flame retardancy while maintaining excellent scratch resistance of pencil hardness HB or more. On the other hand, Comparative Examples 1 and 2 using phosphorus-containing compounds or halogen-based compounds alone could not achieve the desired flame retardancy and scratch resistance. Comparative Example 3 having a high PMMA content was significantly inferior in flame retardancy, and Comparative Example 5 having a high PC content was found to have a lower pencil hardness.

In the present invention, by mixing and applying a phosphorus compound and a halogen compound to a base resin containing a polycarbonate resin and an alkyl (meth) acrylate resin in an appropriate ratio, it is excellent in scratch resistance and flame retardancy, and excellent in impact strength. It has the effect of the invention which provides the scratch-resistant flame retardant thermoplastic resin composition which can express primary colors, such as high black.

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 (11)

(A) 20 to 80% by weight of (a ₁ ) polycarbonate resin; And (a ₂ ) 100 parts by weight of a base resin composed of 20 to 80 wt% of an alkyl (meth) acrylate resin; (B) 1 to 30 parts by weight of the phosphorus compound; And (C) 1 to 30 parts by weight of a halogen compound; Scratch-resistant flame-retardant thermoplastic resin composition comprising a. The scratch flame retardant thermoplastic resin composition of claim 1, wherein the alkyl (meth) acrylate resin is a polymethyl methacrylate resin (PMMA). The method of claim 1, wherein the phosphorus-based compound is phosphate (Phosphate), phosphonate (Phosphonate), phosphinate (Phosphinate), phosphine oxide (Phosphine Oxide), phosphazene (Phosphazene), metal salts thereof Scratch-resistant flame retardant thermoplastic resin composition, characterized in that selected from the group consisting of. The scratch-resistant flame retardant thermoplastic resin composition of claim 1, wherein the phosphorus compound is an aromatic phosphate ester compound represented by the following Chemical Formula 2: [Formula 2]

In the above formula, R _1, R _2, R _4, R ₅ may be independently applied to each other as an aryl group or alkyl-substituted aryl group of C ₆ ~ C ₂₀ , R ₃ is resorcinol, hydroquinol, bisphenol-A , One derived from bisphenol-S, n is 0-5. According to claim 1, wherein the halogen-based compound is decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol A- epoxy oligomer, tribromophenol triazine, brominated polystyrene and their Scratch-resistant flame retardant thermoplastic resin composition, characterized in that selected from the group consisting of a mixture. The scratch-resistant flame retardant thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises 1 to 30 parts by weight of the impact modifier (D) based on 100 parts by weight of the base resin. The scratch-resistant flame retardant thermoplastic resin composition of claim 6, wherein the impact modifier is a rubber-modified graft copolymer or an olefin copolymer. The rubber-modified graft copolymer according to claim 7, wherein the rubber-modified graft copolymer is styrene or alpha-methyl styrene in a rubbery polymer obtained by polymerizing at least one rubber monomer selected from the group consisting of diene rubber, acrylate rubber, and silicone rubber monomer. , Alkyl substituted styrenes; Acrylonitrile, methacrylonitrile; Methyl methacrylate; Maleic anhydride; The scratch-resistant flame-retardant thermoplastic resin composition prepared by graft polymerization of a monomer selected from the group consisting of alkyl or phenyl nucleosubstituted maleimide and mixtures thereof. The scratch-resistant flame retardant thermoplastic resin composition of claim 8, wherein the rubber-modified graft copolymer is a resin (MBS resin) prepared by graft copolymerization of methyl methacrylate and styrene on butadiene rubber. The method of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of anti-dripping agents, antioxidants, plasticizers, thermal stabilizers, light stabilizers, compatibilizers, pigments, dyes, inorganic additives and mixtures thereof. Scratch-resistant flame retardant thermoplastic resin composition. The pellet which extruded the resin composition of any one of Claims 1-10.