KR100373213B1 - Transparent styrenic resins composition having superior fireproof properties - Google Patents

Abstract

The present invention relates to a styrene resin composition, and more particularly to a transparent flame retardant styrene resin composition excellent in impact resistance, processability and transparency as well as flame retardancy.

The present invention provides a transparent flame retardant styrene resin composition excellent flame retardancy for this purpose, a) i) 5 to 20 parts by weight of butadiene rubber or styrene-butadiene copolymer rubber; Ii) 20 to 50 parts by weight of styrene monomer; And iii) 100 parts by weight of a transparent rubber-modified styrene resin including 30 to 65 parts by weight of an acrylic ester monomer; And b) 5 to 30 parts by weight of a triazine compound as a flame retardant.

The present invention has the effect of providing a transparent flame retardant styrene resin composition having particularly excellent flame retardancy while maintaining impact resistance, processability, and transparency.

Description

Transparent flame retardant styrene resin composition excellent in flame retardancy {TRANSPARENT STYRENIC RESINS COMPOSITION HAVING SUPERIOR FIREPROOF PROPERTIES}

[Industrial use]

The present invention relates to a styrene resin composition, and more particularly to a transparent flame retardant styrene resin composition excellent in impact resistance, processability and transparency as well as flame retardancy.

[Private Technology]

Recently, as life patterns and desires of consumers are diversified and plastic materials are used for various purposes, many studies have been conducted to impart high functionality such as transparency to plastic materials in order to differentiate product models. 3,787,522, Japanese Patent Laid-Open No. 63-42940A2, and European Patent Publication No. 0,703,252A2. This is because transparency is often required for products produced and consumed in recent years such as computer monitors, PCS transparent windows, microwave transparent windows, audio transparent windows, game machine housings, and office equipment transparent windows. In addition, in the case of electrical and electronic parts, it is required to use a flame retardant resin to secure safety against fire, and in many cases, it is legally required to use a material having such a property. Required.

However, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) copolymer resins conventionally used for these components have excellent impact resistance, chemical resistance, processability and surface gloss, but are opaque materials due to the characteristics of the resins. This required material has limitations in use and lacks flame retardancy.

In order to overcome this problem, a method of including polybrominated diphenyl ether so that ABS resin has transparency and flame retardancy is known (US Pat. No. 4,581,403), but this method has a limitation in obtaining an extremely transparent resin. .

In addition, tetrabromobisphenol a, brominated epoxy oligomer, bistribromophenoxy ethane, decabromo diphenyl ether, and octabromo diphenyl ether, which are conventionally used as a flame retardant, have transparency due to a difference in refractive index with a transparent ABS resin. It is difficult to express.

On the other hand, in the case of polystyrene resin, methyl methacrylate (Japanese Patent Laid-Open No. 62-127333A, No. 62-116648A2) or copolymerization with methacrylic acid (Japanese Laid-Open Patent Publication) 6-157849A) is known, but has a very weak impact resistance.

Polycarbonate is currently known as a thermoplastic resin having transparency and flame retardancy at the same time as polycarbonate, which has excellent transparency and impact resistance at room temperature, but has weak chemical resistance and poor low temperature impact resistance. There is a limit to the application.

An object of the present invention is to provide a flame retardant styrene resin composition having excellent flame retardancy and transparency while maintaining physical properties such as impact resistance, chemical resistance and processability, in consideration of the problems of the prior art.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a transparent flame-retardant styrene resin composition excellent in flame retardancy,

a) 5 to 20 parts by weight of butadiene rubber or styrene-butadiene copolymer rubber;

Ii) 20 to 50 parts by weight of styrene monomer; And

Iii) 30 to 65 parts by weight of acrylic ester monomer

100 parts by weight of a transparent rubber-modified styrene-based resin comprising; And

b) 5 to 30 parts by weight of a triazine-based compound represented by Formula 1 as a flame retardant

It provides a resin composition comprising:

[Formula 1]

Hereinafter, the present invention will be described in detail.

[Action]

The flame retardant styrene resin composition excellent in transparency and flame retardancy of the present invention comprises a) 100 parts by weight of a transparent rubber-modified styrene resin and b) 5 to 30 parts by weight of a triazine compound as a flame retardant.

As a flame retardant, c) a triazine compound may be used by mixing c) a phosphorus compound, and may further include d) antimony pentoxide as a flame retardant to obtain a flame retardant styrene resin composition having high flame retardance while maintaining transparency.

A) the transparent rubber-modified styrene-based resin is iii) 5 to 20 parts by weight of butadiene rubber or styrene-butadiene copolymer rubber; Ii) 20 to 50 parts by weight of styrene monomer; And iii) 30 to 65 parts by weight of an acrylic ester monomer is prepared by continuous bulk polymerization at 110 to 160 ° C.

The transparency of the a) transparent rubber-modified styrene-based resin depends on the refractive index, the refractive index of the polymer is controlled by the amount of the monomer used and the mixing ratio. That is, in order to have transparency, the refractive index of each of the above-described butadiene rubber or styrene-butadiene copolymer rubber, ii) styrene monomer, and iii) acrylic acid ester monomer to be polymerized should be similar, so that the final composition exhibits excellent transparency. The amount of the monomer used and the mixing ratio are important.

The a) ii) styrene monomer is selected from the group consisting of styrene, methyl styrene, t-butyl styrene, and p-methyl styrene.

The a) i) acrylic acid ester monomer is selected from the group consisting of methyl methacrylate, butyl acrylate, butyl methacrylate, and ethyl acrylate.

The triazine flame retardant of b) is a flame retardant capable of imparting flame retardancy while maintaining the transparency of the transparent rubber modified styrene resin, and is subject to a difference in refractive index with the transparent rubber modified styrene resin which appears when the conventional flame retardant described above is used. It is a flame retardant that can overcome the decrease in transparency. The triazine flame retardant uses 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine represented by Chemical Formula 1.

The b) triazine flame retardant is used 5 to 30 parts by weight based on 100 parts by weight of the transparent rubber modified resin. This is because if the amount of the triazine-based flame retardant used is 5 parts by weight or less, the flame retardant effect is insufficient, and when it is used at 30 parts by weight or more, it may cause a decrease in mechanical strength.

As a flame retardant, the b) triazine compounds alone, as well as c) phosphorus compounds may be used in admixture. Phosphorus-based flame retardant may be a compound represented by the formula 2 to 5, respectively, specifically, triphenyl phosphate (Formula 6), lysosinol tetraphenyldiphosphate (Formula 7), bisphenol tetraphenyldiphosphate (Formula 8) , Ammonium polyphosphate (Formula 9) Etc. can be illustrated. At this time, it is preferable to use 5 to 30 parts by weight of the phosphorus-based flame retardant.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, R ₁ to R ₁₁ are each C ₆ to C ₂₀ aryl group including C ₁ to C ₈ alkyl group or substituted alkyl group, m and n are each an integer of 1 or more.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The antimony pentoxide of d) is a flame retardant that can synergize with the b) triazine flame retardant and the c) phosphorus flame retardant to obtain a high flame retardancy, and the antimony trioxide used as a flame retardant adjuvant due to the large particles of transparent rubber modified Even when a small amount is applied to the resin, it is possible to solve the disadvantage that the transparency of the resin is sharply lowered. In other words, in order to maintain transparency while providing high flame retardancy, it is preferable to use fine antimony pentoxide having a particle size of 5 to 30 nm because transparency can be maintained because there is no diffraction and scattering phenomenon in the visible wavelength range.

The antimony pentoxide is preferably used in an amount of 1 to 15 parts by weight or less based on 100 parts by weight of the a) transparent rubber-modified styrene resin.

Flame retardant styrene resin composition excellent in transparency and flame retardancy of the present invention is a) 100 parts by weight of a transparent rubber-modified styrene resin and b) 5 to 30 parts by weight of triazine-based compound as a flame retardant e) 2 parts by weight or less of antioxidant, And f) 5 parts by weight or less of lubricant.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Examples 1 to 3

100 parts by weight of the transparent rubber-modified styrene-based resin (please specify the specific product name or manufacturing process) 0.1 parts by weight of antioxidant, 0.2 parts by weight of lubricant, and 3 parts by weight of triazine flame retardant, respectively, as shown in Table 1; The mixture to which 4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine was added was uniformly mixed through a Henschel mixer, then pelletized through a twin screw extruder and again The specimen was prepared by injection. The prepared specimens were measured for transparency and flame retardancy, and the results are shown in Table 1.

At this time, transparency was determined by ASTM D1003 test method, and flame retardancy was determined by UL-94 test method.

Examples 4-7

In the same manner as in Examples 1 to 3, a phosphorus flame retardant was used together with 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine as a triazine flame retardant. Specimens were prepared by adding in the compositions shown in Table 1. The prepared specimens were measured for transparency and flame retardancy in the same manner as in Examples 1 to 3, and the results are shown in Table 1.

Comparative Examples 1 to 3

The specimens were prepared in the same manner as in Examples 1 to 4, except that flame retardants were not used as in the composition shown in Table 2, or that decabromodiphenyl ether or brominated epoxyoxy oligomer triphenyl phosphate, which was used in the past, was added. . The prepared specimens were measured for transparency and flame retardancy in the same manner as in Examples 1 to 3 and the results are shown in Table 2.

Comparative Example 4

Samples were prepared in the same manner as in Examples 1 to 4, but using general-purpose polystyrene resins (grade name: 15 NFI, manufactured by LG Chemical Co., Ltd.) rather than transparent rubber-modified styrene resins as shown in Table 2. The prepared specimens were measured for transparency and flame retardancy in the same manner as in Examples 1 to 3 and the results are shown in Table 2.

Example 8

The test was carried out in the same manner as in Examples 1 to 4, but as shown in Table 3, antimony pentoxide, a flame retardant aid, was added together with the flame retardant to prepare a specimen. The prepared specimens were measured for transparency and flame retardancy in the same manner as in Examples 1 to 3, and the results are shown in Table 3.

Comparative Example 5

In the same manner as in Examples 1 to 4, but as shown in Table 3 was added to the flame retardant adjuvant antimony trioxide conventionally used to prepare a specimen. The prepared specimens were measured for transparency and flame retardancy in the same manner as in Examples 1 to 3, and the results are shown in Table 3.

TABLE 1

Classification (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Transparent rubber modified styrene resin 100 100 100 100 100 100 100 Flame retardant 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine 10 15 25 10 10 10 10 Triphenylphosphate - - - 5 - - - Lysosinol Tetraphenyldiphosphate - - - - 8 - - Bisphenoltetraphenyldiphosphate - - - - - 10 - Ammonium Polyphosphate - - - - - - 10 Property transparency 87 85 82 74 76 75 72 Impact strength 7.2 7.0 6.5 6.5 6.4 6.8 6.7 Flame Retardant 1/8 " NR V-2 V-2 V-2 V-2 V-2 V-2 Flame Retardant 1/116 " NR V-2 V-2 V-2 V-2 V-1 V-2

NR: NO RATING

TABLE 2

Classification (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Transparent rubber modified styrene resin 100 100 100 - General purpose polystyrene resin (manufactured by LG Chem, 15NFI) - - - 100 Flame retardant 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine - - - 20 Decabromodiphenyl ether - 15 - - Brominated Epoxy Oligomertriphenyl Phosphate - - 15 - Property transparency 90 10 10 80 Impact strength 7.6 6.5 6.4 1.2 Flame Retardant 1/8 " NR V-2 V-2 V-2 Flame Retardant 1/116 " NR V-2 V-2 V-2

TABLE 3

Classification (parts by weight) Example 8 Comparative Example 5 Transparent rubber modified styrene resin 100 100 Flame retardant 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine 25 25 Flame Retardant Supplements Antimony pentoxide 6 - Antimony trioxide - 6 Property transparency 57 10 Flame Retardant 1/8 " V-0 V-0 Flame Retardant 1/16 " V-0 V-0

As shown in Table 1, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-tri as a transparent rubber-modified styrene resin and a flame retardant prepared according to the present invention. When using 10 to 25 parts by weight of azine alone (Examples 1 to 3) or when using 15 parts by weight or less of phosphorus-based flame retardant together with the triazine (Examples 4 to 7), high transparency and excellent impact strength are maintained. And when used more than 15 parts by weight, V-2 class flame retardancy was obtained.

In contrast, when only transparent rubber-modified styrene resin is used (Comparative Example 1), as shown in Table 2, when the flame retardancy is insufficient and the decabromodiphenyl ether or brominated epoxy oligomer used as a flame retardant is used. In (Comparative Examples 2 and 3), transparency was sharply decreased, and when general-purpose polystyrene was used instead of the transparent rubber-modified styrene resin (Comparative Example 4), transparency was expressed, but it was found that the impact strength was very weak.

In addition, when the antimony pentoxide is added as a flame retardant adjuvant (Example 8) as shown in Table 3, the transparency is slightly reduced, but can achieve a V-0 grade flame retardancy, compared with the use of antimony trioxide (Comparative Example) 5) The flame retardancy of V-0 level is secured, but the transparency is almost absent.

The present invention has the effect of providing a transparent flame retardant styrene resin composition having particularly excellent flame retardancy while maintaining impact resistance, processability, and transparency.

Claims (7)

In the transparent flame retardant styrene resin composition excellent in flame retardancy, a) 5 to 20 parts by weight of butadiene rubber or styrene-butadiene copolymer rubber; Ii) 20 to 50 parts by weight of styrene monomer; And Iii) 30 to 65 parts by weight of acrylic ester monomer 100 parts by weight of a transparent rubber-modified styrene-based resin comprising; And b) 5 to 30 parts by weight of a triazine-based compound represented by Formula 1 as a flame retardant Resin composition comprising: [Formula 1] The method of claim 1, In the composition c) 5 to 30 parts by weight of a phosphorus compound selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 5 as a flame retardant Resin composition further comprising: [Formula 2] [Formula 3] [Formula 4] [Formula 5] In Formulas 2 to 5, R ₁ to R ₁₁ are C ₆ to C ₂₀ aryl groups each containing a C ₁ to C ₈ alkyl group or a substituted alkyl group, and m and n are each an integer of 1 or more. The method of claim 1, In the composition d) 1 to 15 parts by weight of antimony pentoxide having a particle size of 5 to 30 nm as a flame retardant aid. Resin composition further comprising. The method of claim 1, In the composition e) 2 parts by weight or less of antioxidant Resin composition further comprising. The method of claim 1, In the composition f) 5 parts by weight or less of lubricant Resin composition further comprising. The method of claim 1, The resin composition of the said a) ii) styrene-type monomer is selected from the group which consists of styrene, methylstyrene, t-butyl styrene, and p-methyl styrene. The method of claim 1, The resin composition of the above-mentioned a) iii) acrylic acid ester monomer is selected from the group consisting of methyl methacrylate, butyl acrylate, butyl methacrylate, and ethyl acrylate.