KR20090066624A - Thermaplastic flame retardant resin composition improved scratch resistance - Google Patents

Abstract

A flame retardant thermoplastic resin composition is provided to improve scratch resistance, thereby preventing the inferiority of appearance even under various molding conditions. A flame retardant thermoplastic resin composition comprises 10 ~ 30 parts by weight of the rubber-modified styrene resin prepared from a styrene-based monomer and a rubber polymer; 10 ~ 30 parts by weight of a copolymer prepared from a styrene-based monomer, an acrylate-based monomer and an acrylonitrile-based monomer; 1 ~ 15 parts by weight of a styrene-based olefin-based block copolymer; 4 ~ 25 parts by weight of a halogen-based flame retardant; and 0.5 ~ 10 parts by weight of a flame retardant aid.

Description

Thermoplastic flame retardant resin composition with improved scratch resistance {THERMAPLASTIC FLAME RETARDANT RESIN COMPOSITION IMPROVED SCRATCH RESISTANCE}

The present invention relates to a thermoplastic flame-retardant resin composition with improved scratch resistance, and more specifically, it can be applied to various fields without appearance defects under a variety of molding conditions, excellent flame resistance and impact resistance is maintained, scratch resistance, gloss The present invention relates to a thermoplastic flame-retardant resin composition with improved degree and chemical resistance.

Rubber modified styrene resins, which are represented by impact-resistant polystyrene resins, have excellent moldability, stiffness, and electrical characteristics, so that OA devices such as word processors, personal computers, printers, and copiers, televisions (TVs), and video (VTR) ), It is widely used in various industries including home appliances such as audio.

However, the rubber-modified styrene resin has a property that is easy to burn in spite of excellent processability and physical properties, and thus has been a problem for stability, and thus studies have been made to give flame retardancy to rubber-modified styrene resin.

Currently, rubber modified styrene resins are kneaded together with halogen flame retardants and flame retardants to impart flame retardancy (combustion suppression by radical trapping effect in gas phase during combustion) and rubber modified styrene resins are non-halogen flame retardants, namely A method of kneading with a phosphorus-based or nitrogen-based flame retardant to impart flame retardancy (a method of suppressing combustion by a char barrier film formed during combustion) or the like is generally used.

However, as consumer's life patterns and desires have been diversified and product differentiation has been recently made, various other physical properties such as high hardness, scratch resistance, colorability, chemical resistance, etc. are required in addition to the simple flame retardancy of resin for electrical and electronic product housing. In order to provide such characteristics, Japanese Patent Laid-Open No. 62-127333, Japanese Patent Laid-Open No. 62-116648, and Japanese Patent Laid-Open No. Hei 6-157849 disclose a method of using a flame retardant in a resin copolymerized with styrene and methyl methacrylate or methacrylic acid. There is a disadvantage that the impact resistance is extremely reduced. In order to overcome such drawbacks, Korean Patent Laid-Open Publication No. 2002-0043819 discloses a method of improving impact resistance by injecting a rubber polymer during copolymerization of styrene and methyl methacrylate, but has a disadvantage in that chemical resistance is lowered.

In addition, a method of mixing a polycarbonate and a flame retardant with an acrylonitrile-butadiene-styrene copolymer has also been disclosed, but there is a limit in application to large parts due to the lack of processability.

In order to solve the problems of the prior art as described above, the present invention can be applied to various fields because there is no defect in the appearance even under various molding conditions, excellent flame resistance and impact resistance is maintained, scratch resistance, gloss and chemical resistance, etc. It is an object to provide an improved thermoplastic flame retardant resin composition.

In order to achieve the above object, the present invention comprises a) 100 parts by weight of a rubber-modified styrene resin composed of a styrene monomer and a rubber polymer; b) 10 to 30 parts by weight of a copolymer prepared from styrene monomer, acrylate monomer and acrylonitrile monomer; c) 1 to 15 parts by weight of styrene-olefin block copolymer; d) 4 to 25 parts by weight of halogen-based flame retardant; And e) 0.5 to 10 parts by weight of a flame retardant adjuvant; provides a thermoplastic flame retardant resin composition having improved scratch resistance.

According to the present invention, by including styrene-acrylate-acrylonitrile-based copolymers, etc., there are no defects in appearance even under various molding conditions, can be applied to various fields, excellent flame resistance and impact resistance is maintained, scratch resistance, There is an effect of providing a thermoplastic flame retardant resin composition with improved gloss and chemical resistance.

Hereinafter, the present invention will be described in detail.

The thermoplastic flame retardant resin composition having improved scratch resistance of the present invention comprises a) 100 parts by weight of a rubber-modified styrene resin prepared from a styrene monomer and a rubber polymer; b) 10 to 30 parts by weight of a copolymer prepared from styrene monomer, acrylate monomer and acrylonitrile monomer; c) 1 to 15 parts by weight of styrene-olefin block copolymer; d) 4 to 25 parts by weight of halogen-based flame retardant; And e) 0.5 to 10 parts by weight of a flame retardant adjuvant.

The rubber-modified styrene resin of a) used in the present invention serves to support the strength of the molded article manufactured by molding the rubber-modified styrene resin as a main component of the thermoplastic flame-retardant resin composition.

The rubber-modified styrene resin is formed by dispersing a rubber polymer in the form of particles on a matrix made of a polymer polymerized with a styrene monomer.

The polymerization method of the rubber-modified styrene-based resin may be all of the conventional bulk polymerization method, suspension polymerization method, emulsion polymerization method and the like, but is preferably using a bulk polymerization method. As a specific example, during the bulk polymerization, the rubber polymer may be dissolved in a styrene-based monomer and then polymerized by adding a polymerization initiator while stirring.

The rubber modified styrene resin may be prepared by further including a comonomer during polymerization.

The styrene monomer is styrene; nuclear alkyl substituted styrenes such as p-methylstyrene, 2,4-dimethylstyrene and ethyl styrene; And? -Alkyl substituted styrenes such as? -Methyl-p-methylstyrene and the like.

The rubber polymer is preferably a rubber polymer (soft component particles, high cis-butadiene) having a cis 1,4-bond of at least 70% by weight of the butadiene chain portion, and more preferably a sheath in the butadiene chain portion. The content of 1,4-bond is 90% by weight or more. If the cis 1,4-bond of the butadiene chain portion of the rubber polymer is less than 70% by weight (low cis-butadiene), there is a problem that the effect of improving impact resistance is insignificant.

The rubber polymer may be a rubber polymer containing polybutadiene, acrylate or methacrylate, styrene-butadiene-styrene copolymer, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, or the like. have. In particular, it is preferable to use polybutadiene or styrene-butadiene copolymer, and more preferably to use polybutadiene.

The copolymer prepared from the styrene-based monomer, acrylate-based monomer and acrylonitrile-based monomer of b) used in the present invention serves to impart scratch resistance, glossiness, chemical resistance, etc. to the rubber-modified styrene resin. And, it is preferably included in 10 to 30 parts by weight based on 100 parts by weight of the rubber modified styrene resin. If the content is less than 10 parts by weight, there is a problem that the scratch resistance is lowered, if it exceeds 30 parts by weight there is a problem that the flame resistance, impact resistance is lowered.

Styrene-based monomers used for preparing the copolymer of b) is styrene; nuclear alkyl substituted styrenes such as p-methylstyrene, 2,4-dimethylstyrene and ethyl styrene; And α-alkyl substituted styrenes such as α-methyl-p-methylstyrene and the like.

As the acrylate monomer, at least one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate may be used.

As the acrylonitrile-based monomer, one or more selected from the group consisting of acrylonitrile, methacrylonitrile and etaacrylonitrile may be used.

The styrene-olefin block copolymer of c) used in the present invention is composed of at least one styrene block and at least one olefin block, and is in the form of a styrene-olefin block and a styrene-olefin-styrene block. It includes all block type, olefin-styrene-olefin block type and the like.

Examples of the styrene monomer used in the styrene block include styrene; nuclear alkyl substituted styrenes such as p-methylstyrene, 2,4-dimethylstyrene and ethyl styrene; And α-alkyl substituted styrenes such as α-methyl-p-methylstyrene and the like.

The olefinic monomers used in the olefinic block are selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, butadiene, isoprene, 1,3-pentadiene, 1,4-hexadiene, norbornene derivatives, and the like. One or more selected species may be used. In addition, a styrene compound may be copolymerized randomly in an olefin block.

The styrene-olefin-based block copolymer of c) acts as an impact modifier for imparting impact resistance to the rubber-modified styrene-based resin, and includes 1 to 15 parts by weight based on 100 parts by weight of the rubber-modified styrene-based resin. It is desirable to be. If the content is less than 1 part by weight, there is a problem that the impact resistance is lowered. If the content is more than 15 parts by weight, the rigidity and heat resistance are lowered.

The halogen-based flame retardant of d) used in the present invention is one or more compounds selected from organic halogen-based compounds, may be used by mixing two or more.

The organic halogen-based compound includes an organic chlorine-based compound, an organic bromine-based compound, and the like, of which an organic bromine-based compound is particularly excellent in imparting flame retardancy. Examples thereof include brominated phenol resins, brominated diphenyl oxide resins, brominated epoxy resins, and brominated imide resins.

More specific examples of flame retardants that may be used in the present invention include decabromodiphenyl oxide, testabromo bisphenol A, tetrabromo bisphenol A epoxy resin, tetrabromo bisphenol A carbonate oligomer, tetrabromo bisphenol A-bis (2- Hydroxy ethyl ether), tetrabromo bisphenol A-bis (2,3-dibromopropyl ether), tetrabromo bisphenol A-bis (allyl ether), brominated triazine, tribromo phenylallyl ether, tribro Monopentyl alcohol, bis (2,4,6-tribromo phenoxy) ethane, polydibromophenylene ether, tetrabromo cyclooctane, brominated polyethylene, ethylene bis tetrabromo phthalimide, ethylene bispenta Bromodiphenyl, hexabromo cyclo rodecan, hexa bromo benzene, octabromo diphenylether, octabromodiphenyl oxide, tris (2,3-dibromorph Phil) include isocyanurate, tetrabromo bisphenol S, penta-bromotoluene.

The flame retardant adjuvant of e) used in the present invention causes a flame retardant synergism with the halogen-based flame retardant, and may be at least one selected from antimony trioxide, antimony pentoxide, metal antimony, antimony trichloride, and the like. In this case, antimony trioxide is particularly excellent in flame retardant synergism.

The thermoplastic flame-retardant resin composition of the present invention comprising the above components may further include additives such as antioxidants, heat stabilizers, light stabilizers, lubricants, inorganic additives, pigments, and the like, as necessary.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example  One

<Rubber denaturation Styrene series  Manufacturing of Resin>

After preparing a monomer solution consisting of 8 parts by weight of butadiene rubber, 77 parts by weight of styrene, and 15 parts by weight of ethylene, a 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane was used as a polymerization initiator. 0.02 parts by weight was added.

The mixed solution was introduced into a continuous polymerization apparatus in which four stirred reactors were connected in series and continuously graft copolymerized. At this time, the inlet temperature of the continuous polymerization apparatus was 125 ° C and the outlet temperature was 140 ° C.

The final copolymerized mixed solution was sent to a devolatilization tank to remove unreacted monomers and solvents at 230 ° C. and 20 torr, and then pelletized to give a rubber-modified styrene resin containing 8% by weight of rubber. HIPS) was prepared.

<Production of thermoplastic flame retardant resin>

15 parts by weight of LG Chem's XT510, a copolymer made from styrene, acrylonitrile and methyl methacrylate (hereinafter referred to as SAMMA), in 100 parts by weight of the rubber-modified styrene-based resin prepared above, was used as an impact reinforcing material. Use 5 parts by weight of LG Chem 604P, a styrene block copolymer (SBS), 20 parts by weight of SR245 from Daiichi, a brominated triazine compound, 4 parts by weight of antimony trioxide as a flame retardant, and 4 parts by weight of poly 0.01 parts by weight of tetrafluoroethylene, 0.6 parts by weight of zinc stearate and 0.6 parts by weight of calcium stearate and 0.5 parts by weight of antioxidant were added. The mixture was uniformly mixed with a Henschel mixer, then extruded at 210 ° C. using a twin screw extruder to produce pellets, and then injected again to prepare specimens.

Example  2

Except for using 25 parts by weight of SAMMA in Example 1 was carried out in the same manner as in Example 1.

Example  3

Except for using 15 parts by weight of Saytex 102E, which is a decabromodiphenyl oxide of Albemarle, and 5 parts by weight of antimony trioxide in Example 1, Albemarle was used in the same manner as in Example 1.

Comparative example  One

Except for using the SAMMA in Example 1 was carried out in the same manner as in Example 1.

Comparative example  2

Except for using 40 parts by weight of SAMMA in Example 1 was carried out in the same manner as in Example 1.

Comparative example  3

In Example 1, except that 15 parts by weight of the polymethyl methacrylate (hereinafter PMMA) DOW IH830 instead of SAMMA was used in the same manner as in Example 1.

Comparative example  4

In the same manner as in Example 1, except that 100 parts by weight of HI121H of LG Chemical, which is an acrylonitrile-butadiene-styrene copolymer (hereinafter ABS), was used instead of HIPS, and SBS was not used. Was carried out.

Using the thermoplastic flame-retardant resin prepared in Examples 1 to 3 and Comparative Examples 1 to 4 by the following method to measure scratch resistance, gloss, chemical resistance, impact resistance, flowability, and flame retardancy, and the results Table 1 shows.

A) Scratch resistance-measured according to ASTM D3363.

B) Glossiness-measured at 45 ° according to ASTM D2457.

C) Chemical resistance-A 3.2 mm thick bar prepared by injection molding was fixed to a jig (R: 226.97 mm) at both ends, and then soybean oil was added to the gauze. After being buried, it was placed in the center of the specimen and allowed to soak in the specimen for 24 hours. After 24 hours, changes in the surface appearance and cracks of the specimen were visually checked and the thickness was measured and compared (◎: no change, ○: color change, △: cracking / surface change was severe, × : can not be used).

D) Impact resistance—Izod impact strength (kg · cm / cm) was measured with a notched specimen of thickness 1/8 ”according to ASTM D256.

ㅁ) Fluidity-measured under conditions of 200 ° C. and 5 kg in accordance with ASTM D1238.

Viii) Flame retardancy-measured on a 1/16 "specimen according to the UL-94 test method.

division Example Comparative example One 2 3 One 2 3 4 HIPS 100 100 100 100 100 100 ABS 100 SAMMA 15 25 15 0 40 PMMA 15 15 SBS 5 5 5 5 5 5 - Tribromide compounds 20 20 - 20 20 20 20 Decabromo diphenyloxide - - 15 - - - - Antimony trioxide 3 3 5 3 3 3 3 Scratch resistance F H F 2B H ~ 2H H F Glossiness 90 92 86 68 95 91 92 Chemical resistance ○ ◎ ○ △ ◎ ○ ○ Impact resistance 10 8 9 12 4 4 18 liquidity 14 12 10 16 7 9 4 Flame retardant V-0 V-0 V-0 V-0 V-2 V-2 V-0

As shown in Table 1, the thermoplastic flame-retardant resin composition (Examples 1 to 3) prepared by using a bromide triazine and decabromodiphenyl oxide compound as a flame retardant while using a proper amount of SAMMA according to the present invention V in flame retardancy It showed excellent flame retardancy of -0 grade, and it was confirmed that physical properties such as scratch resistance, gloss resistance, and chemical resistance were improved while maintaining excellent impact resistance and fluidity.

On the other hand, Comparative Example 1, which does not contain SAMMA, has excellent impact resistance, fluidity, and the like, but scratch resistance, glossiness, and chemical resistance are lowered. In Comparative Example 2, in which an excessive amount of SAMMA is added, scratch resistance and chemical resistance Excellent, but did not achieve the V-0 flame retardancy, it was confirmed that the impact resistance is significantly reduced.

In addition, in the case of Comparative Example 3 in which PMMA was added instead of SAMMA, it was confirmed that not only the flame retardancy of the V-0 grade was achieved but also the impact resistance was reduced.

Finally, in the case of Comparative Example 4 using the ABS resin instead of HIPS, the overall physical properties were good, but it was confirmed that the fluidity is seriously reduced.

Claims (10)

a) 100 parts by weight of a rubber modified styrene resin prepared from a styrene monomer and a rubber polymer; b) 10 to 30 parts by weight of a copolymer prepared from styrene monomer, acrylate monomer and acrylonitrile monomer; c) 1 to 15 parts by weight of styrene-olefin block copolymer; d) 4 to 25 parts by weight of halogen-based flame retardant; And e) 0.5 to 10 parts by weight of a flame retardant adjuvant; characterized in that comprises Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1, The styrene monomers of a), b) and c) are at least one member selected from the group consisting of styrene, p-methylstyrene, 2,4-dimethylstyrene, ethyl styrene and α-methyl-p-methyl styrene. By Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1 The rubber polymer of a) comprises a rubber polymer containing polybutadiene, acrylate or methacrylate, styrene-butadiene-styrene copolymer, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer and natural rubber At least one member selected from the group Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1, The acrylate monomer of b) is at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1, The acrylonitrile monomer of b) is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and etaacrylonitrile. Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1, The styrene-olefin block copolymer of c) is characterized in that at least one styrene block and at least one olefin block are bonded to each other. Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 6, The olefin block is at least one member selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, butadiene, isoprene, 1,3-pentadiene, 1,4-hexadiene and norbornene derivatives. doing Thermoplastic flame retardant resin composition with improved scratch resistance.        The method of claim 1, The halogen flame retardant of d) is decabromodiphenyl oxide, Teslabromo bisphenol A, tetrabromo bisphenol A epoxy resin, tetrabromo bisphenol A carbonate oligomer, tetrabromo bisphenol A-bis (2-hydroxy ethyl Ether), tetrabromo bisphenol A-bis (2,3-dibromopropyl ether), tetrabromo bisphenol A-bis (allyl ether), brominated triazine, tribromo phenylallyl ether, tribromo neopentyl Alcohol, bis (2,4,6-tribromo phenoxy) ethane, polydibromophenylene ether, tetrabromo cyclooctane, brominated polyethylene, ethylene bis tetrabromo phthalimide, ethylene bis pentabromodiphenyl , Hexabromo cyclodecane, hexa bromo benzene, octabromo diphenyl ether, octabromodiphenyl oxide, tris (2,3-dibromo propyl) isocyanurate, te Rab our bisphenol, characterized in that at least one member selected from S and penta bromo group consisting of Mo toluene Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1 The flame retardant adjuvant of e) is at least one member selected from the group consisting of antimony trioxide, antimony pentoxide, metal antimony and antimony trichloride. Thermoplastic flame retardant resin composition with improved scratch resistance. The method of claim 1, The thermoplastic flame-retardant resin composition further comprises one or more selected from the group consisting of dropping regulator, antioxidant, heat stabilizer, light stabilizer, lubricant, inorganic additive and pigment. Thermoplastic flame retardant resin composition with improved scratch resistance.