KR100797576B1 - Flame retardant thermoplastic resin compositoin comprising organic peroxide, and a method for preparing the same by using organic peroxide - Google Patents

Abstract

The present invention relates to a thermoplastic flame-retardant resin composition, and a method for manufacturing the same, and more particularly, 5 to 80 parts by weight of a rubber-modified styrenic graft copolymer, and 95 to 20 parts by weight of a styrenic copolymer. It relates to a thermoplastic flame-retardant resin composition comprising 0.01 to 10 parts by weight of the organic peroxide relative to parts by weight and a method for producing the same.

The thermoplastic flame-retardant resin composition of the present invention does not contain a halogen-based compound, and has excellent properties of flame retardancy and mechanical properties by using an organic peroxide in a mixed resin of a rubber-modified styrene graft copolymer and a styrene copolymer.

Non-halogen, thermoplastic, flame retardant, organic peroxide, nanoclay, ABS resin

Description

Thermoplastic flame retardant resin composition comprising an organic peroxide, and a method for producing the same using organic peroxides

[Industrial use]

The present invention relates to a thermoplastic flame-retardant resin composition, and to a method for manufacturing the same, and more particularly, to a non-halogen-based thermoplastic flame-retardant resin composition and a method for producing the same that do not include a halogen-based compound and satisfy the UL94 V-2 grade. .

[Private Technology]

Rubber modified styrene resins have excellent processability and physical properties, have good appearance and excellent impact strength, and are widely used in housing materials for electric and electronic products and office equipment.

In particular, since electrical and electronic products and office equipment generate a lot of heat during use, there is a risk of fire when overheated, so the housing material used therein should have excellent flame retardancy.

As a result of a long study, it is known that the use of halogen-based compounds as flame retardants is the most effective method for flame retardant rubber modified styrene resins. Among them, tetrabromobisphenol A and brominated epoxy are the most commonly used halogen flame retardants, and it is also widely known that antimony compounds play a role of increasing flame retardancy.

However, halogen-based compounds generate gases that corrode molds during processing, and are known to decompose during combustion to release toxic gases harmful to humans. In particular, bromine compounds are controversial because they can generate environmental hormones such as dioxins and furans during combustion, and their use has been restricted in Europe.

In addition, antimony compounds are classified as carcinogens and toxic substances.

Accordingly, much attention has been focused on the research on the composition of the flame retardant resin without using a halogen compound and antimony. Phosphorus-based flame retardants and melamine-based flame retardants are widely used in the composition of flame-retardant resins that do not use halogen compounds and antimony, but have a disadvantage in that flame retardancy is insufficient compared to halogen-based compounds.

In addition, research on flame retardation by various flame retardants has been conducted. U.S. Patent No. 6,677,760 discloses that addition of nanoclays helps prevent dropping of the resin during combustion and improves the LOI (limiting oxygen index). However, nanoclays alone in rubber-modified styrene resins are known. Not enough flame retardancy to achieve UL94 V-2 vertical test rating.

The present invention is to solve the above problems, an object of the present invention is to provide a non-halogen-based thermoplastic flame-retardant resin composition excellent in flame retardancy and mechanical properties of the UL94 V-2 grade.

Another object of the present invention is to provide a method for producing the thermoplastic flame retardant resin composition.

In order to achieve the above object, the present invention provides a thermoplastic flame retardant resin composition in which an organic peroxide, or an organic peroxide and a nanoclay are added and mixed with a rubber-modified styrenic graft copolymer and a basic resin mixture comprising a styrene copolymer. to provide.

The present invention also comprises the steps of: a) preparing a rubber modified styrenic graft copolymer; b) preparing a styrenic copolymer; c) mixing the rubber modified styrene graft copolymer and the styrene copolymer to prepare a basic resin mixture; And d) mixing the organic peroxide, or the organic peroxide and nanoclay in the base resin mixture.

Hereinafter, the present invention will be described in more detail.

The thermoplastic flame-retardant resin composition of the present invention comprises (A) a rubber-modified styrenic graft copolymer, and a base resin mixture comprising a styrene-based copolymer, and (B) an organic peroxide, more preferably (A) the A base resin mixture, (B) said organic peroxide, and (C) nanoclays.

The base resin mixture (A) preferably contains 5 to 80 parts by weight of the rubber-modified styrene graft copolymer, and 95 to 20 parts by weight of the styrene copolymer.

The rubber modified styrene graft copolymer serves to supplement the impact strength of the thermoplastic flame retardant resin composition of the present invention, the styrene copolymer serves to supplement the stiffness, toughness and dimensional stability.

Therefore, when the content of the rubber-modified styrene-based graft copolymer is less than 5 parts by weight, or the content of the sterin-based copolymer exceeds 95 parts by weight, the impact strength may be lowered, the rubber-modified styrene-based graft copolymer When the content of more than 80 parts by weight or the content of the styrene-based copolymer is less than 20 parts by weight, the stiffness and toughness may be lowered and the dimensional stability may be lowered.

In addition, the organic peroxide is preferably included in 0.01 to 10 parts by weight based on 100 parts by weight of the base resin mixture. Organic peroxide is added to improve the flame retardant properties of the resin, when the content is less than 0.01 parts by weight, the effect of improving the flame retardant properties is insignificant, and when it exceeds 10 parts by weight, the impact strength of the thermoplastic resin composition may be lowered. have.

The rubber-modified styrene-based graft copolymer is, based on 100 parts by weight of the rubber-modified styrene-based graft copolymer, a) one or more styrene resins selected from the group consisting of styrene, alpha methyl styrene, and nuclear substituted styrene. 30 to 65 parts by weight; And b) 10 to 30 parts by weight of one or more acrylic resins selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate c) butadiene rubber, styrene-butadiene copolymer, isoprene rubber, and butadiene-isoprene It is preferably prepared by graft polymerization of 10 to 60 parts by weight of one or more rubbery copolymers selected from the group consisting of copolymers, and acrylics prepared by graft polymerization of styrene, acrylonitrile, and butadiene in the above content ratios. It is more preferable that it is ronitrile / butadiene / styrene (ABS) resin.

In addition, the styrenic copolymer is, based on 100 parts by weight of the styrenic copolymer, a) 50 to 90 parts by weight of one or more styrene resins selected from the group consisting of styrene, alpha methyl styrene, and nuclear substituted styrene; And b) 10 to 50 parts by weight of at least one acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate.

The organic peroxide mixed with the base resin is not particularly limited, but ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide It is preferably at least one selected from the group consisting of (diacyl peroxide), peroxy ester, and peroxycarbonate.

The thermoplastic flame retardant resin composition of the present invention may further include a nanoclay. When the nanoclay is used alone and mixed with the base resin, the effect of improving flame retardancy is insignificant, but when used together with the organic peroxide, there is an effect of further improving flame retardancy and mechanical properties. In this case, the content of the nanoclay to be added is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the base resin mixture. If the content of the nanoclay is less than 0.01 parts by weight, the effect of improving flame retardancy is insignificant, and if it exceeds 10 parts by weight, the processability of the resin may be lowered.

The nanoclay means a layered silicate having an interlayer distance of several to several tens of nanometers, and preferably at least one layered silicate selected from the group consisting of montmorillonite, hectorite, vermiculite, and saponite, and organic layered organic layers thereof. Silicates, or mixtures of two or more thereof.

The organic layered silicate is to treat the layered silicate with an organic agent to increase the compatibility with the base resin, and the layered silicate is easily peeled and dispersed in a nanometer size in the base resin, the organicizing agent is alkyl At least one selected from the group consisting of ammonium, alcohols, and ketones is preferable.

In addition, the nanoclays used in the present invention may be used commercially produced nanoclays, it may be used Cloisite 15A, Cloisite 30B, Cloisite 93A, Cloisite 20A, etc., which is a layered silicate product treated with an organic agent.

The thermoplastic flame retardant resin composition of the present invention may further include a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, an anti drip agent, a pigment, an inorganic filler, and the like, as necessary.

Method for producing a thermoplastic flame retardant resin composition of the present invention comprises the steps of: a) preparing a rubber modified styrene-based graft copolymer; b) preparing a styrenic copolymer; c) mixing the rubber-modified styrene graft copolymer and the styrene copolymer to prepare a base resin mixture; And d) mixing the organic peroxide with the base resin mixture, and e) mixing the nanoclay with the base resin mixture.

The step a) of preparing a rubber-modified styrenic graft copolymer is selected from the group consisting of i) styrene, alpha methyl styrene, and nuclear substituted styrene, based on 100 parts by weight of the rubber-modified styrenic graft copolymer. 30 to 65 parts by weight of one or more styrene resins; And ii) 10 to 30 parts by weight of at least one acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate. Iii) Butadiene rubber, styrene-butadiene copolymer, isoprene rubber, and butadiene-isoprene. It is preferable to graft-polymerize 10-60 weight part of 1 or more types of rubbery copolymers chosen from the group which consists of a copolymer.

However, the graft polymerization method is not particularly limited, and may be polymerized according to a conventional method. Preferably, the graft polymerization may be carried out by bulk polymerization or emulsion polymerization.

In addition, the step b) preparing the styrenic copolymer, i) with respect to 100 parts by weight of the styrenic copolymer, i) styrene, alpha methyl styrene, and at least one styrene resin selected from the group consisting of nuclear substituted styrene. 50 to 90 parts by weight; And ii) 10 to 50 parts by weight of at least one acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate.

However, the method of polymerization of the styrene-based copolymer is not particularly limited, and may be polymerized according to a conventional method, and preferably may be polymerized by bulk polymerization or emulsion polymerization.

The preparing of the base resin mixture of step c) may include mixing 5 to 80 parts by weight of the rubber-modified styrenic graft copolymer with 95 to 20 parts by weight of the styrene copolymer based on 100 parts by weight of the base resin mixture. It is desirable to.

In addition, the mixing temperature of the base resin mixture is determined according to the size and type of the mixing device, and does not deviate significantly from the generally known range, and is not particularly limited in the present invention.

The mixing step of the base resin mixture and the mixing of the organic peroxide and the nanoclay may proceed simultaneously or sequentially, and the present invention does not have any particular limitation on the order of addition.

In the step of mixing the organic peroxide of step d), it is preferable to mix 0.01 to 10 parts by weight of the organic peroxide with respect to 100 parts by weight of the base resin mixture.

In addition, the step of mixing the nanoclay of step e) is preferably mixed with 0.01 to 10 parts by weight of nanoclays with respect to 100 parts by weight of the base resin mixture.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

EXAMPLE

Sample Preparation

1) Preparation of rubber-modified styrenic graft copolymer

Acrylonitrile / butadiene / styrene resins in which acrylonitrile and styrene are grafted to butadiene rubber by an emulsion polymerization method such as that disclosed in Korean Patent No. 0358231 (30 wt% styrene, 20 wt% acrylonitrile, and butadiene rubber) 50% by weight) was used.

2) Preparation of Styrene Copolymer

Styrene-based copolymer was used as the SAN 90HR of ㈜ ^® LG Chemical.

3) Preparation of Organic Peroxides

Percumyl D ^® (Dicumyl Peroxide) from NOF (Nippon Oil & Fat Corporation), which is a dialkyl organic peroxide, was used.

4) Preparation of Nanoclay

Nanoclay was used as Cloisite 15A ^® of Southern Clay, organicized with quaternary ammonium salts.

Example 1

40% by weight of the rubber-modified styrenic graft copolymer and 60% by weight of the styrene-based copolymer were mixed in a twin screw extruder to prepare a basic resin mixture.

0.7 parts by weight of Percumyl D, which is an organic peroxide, and 3 parts by weight of Cloisite 15A, which are nanoclays, were added to 100 parts by weight of the base resin mixture, and then mixed in a twin screw extruder to prepare a thermoplastic thermoplastic flame retardant resin composition.

The prepared pellets were injected into the specimens, and the impact strength and flame retardancy were measured by the following method, and the results are shown in Table 1.

* Impact strength

Measurements were made on specimens 1/8 "thick according to ASTM D-256 conditions.

* Flame retardancy

It was measured according to UL94 VB flame retardant standard.

Example 2

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 1 part by weight of Percumyl D and 5 parts by weight of Cloisite 15A were added and mixed with 100 parts by weight of the base resin mixture. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 3

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 3 parts by weight of Percumyl D and 2 parts by weight of Cloisite 15A were added and mixed with 100 parts by weight of the base resin mixture. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 4

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 0.01 part by weight of Percumyl D and 0.01 part by weight of Cloisite 15A were mixed with respect to 100 parts by weight of the base resin mixture. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 5

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 0.01 part by weight of Percumyl D and 10 parts by weight of Cloisite 15A were added and mixed with 100 parts by weight of the base resin mixture. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 6

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 10 parts by weight of Percumyl D and 0.01 parts by weight of Cloisite 15A were added and mixed with 100 parts by weight of the base resin mixture. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 7

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 5 parts by weight of Percumyl D and 5 parts by weight of Cloisite 15A were mixed with respect to 100 parts by weight of the base resin mixture. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 8

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1, except that 10 parts by weight of Percumyl D and 10 parts by weight of Cloisite 15A were added to 100 parts by weight of the base resin mixture, and the impact was carried out in the same manner. The strength and flame retardancy were measured and the results are shown in Table 1.

Example 9

A thermoplastic flame retardant resin composition and a specimen were prepared in the same manner as in Example 3, except that the nanoclay Cloisite 15A was not added. The impact strength and the flame retardancy were measured in the same manner, and the results are shown in Table 1.

Comparative Example 1

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 2 except that Percumyl D, which was an organic peroxide, was used. The impact strength and the flame retardance were measured in the same manner, and the results are shown in Table 1.

Comparative Example 2

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 2, except that Percumyl D, which is an organic peroxide, was used at 0.005 parts by weight. .

Comparative Example 3

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 2, except that 13 parts by weight of organic peroxide D was used. The impact strength and the flame retardance were measured in the same manner, and the results are shown in Table 1. .

Comparative Example 4

A thermoplastic flame-retardant resin composition and a specimen were prepared in the same manner as in Example 1 except that 15 parts by weight of nanoclay Cloisiter 15A was used without using an organic peroxide D, and the impact strength and the flame retardance were prepared in the same manner. The results are shown in Table 1 below.

Comparative Example 5

The thermoplastic flame-retardant resin composition and the specimens were prepared in the same manner as in Example 1, except that 8 parts by weight of aromatic monophosphate TPP (TriPhenylPhosphate, manufactured by Daihachi, Japan) was used as the phosphorus flame retardant, without using organic peroxides and nanoclays. It was prepared, and the impact strength and flame retardancy was measured by the same method and the results are shown in Table 1.

TABLE 1

Impact Strength (kg.cm/cm) Heat Deflection Temperature (℃) Flame Retardant (1/8 ") Example 1 28 83 V-2 Example 2 24 85 V-2 Example 3 21 86 V-2 Example 4 30 83 V-2 Example 5 26 87 V-2 Example 6 18 88 V-2 Example 7 22 86 V-2 Example 8 15 90 V-2 Example 9 22 86 V-2 Comparative Example 1 29 83 N.R Comparative Example 2 29 84 N.R Comparative Example 3 3 85 V-2 Comparative Example 4 - - - Comparative Example 5 27 73 V-2

In Table 1, N.R (No Rating) indicates no flame retardancy.

From the results of Table 1, all of the thermoplastic flame retardant resin compositions prepared according to Examples 1 to 9 of the present invention satisfy the flame retardancy of UL-94 V-2, but do not contain an organic peroxide or have a slight content. It can be seen that the thermoplastic flame retardant resin compositions of Comparative Examples 1 and 2 did not exhibit satisfactory flame retardancy in the UL-94 test.

In addition, when using 10 parts by weight or more of the organic peroxide as in the flame retardant resin composition of Comparative Example 3, the impact strength is lowered, it is difficult to use, when using 10% by weight or more of nanoclays as in Comparative Example 4 during the extrusion kneading process Excessive load was applied to make it difficult to discharge the resin and form the resin.

In addition, when using an aromatic phosphate flame retardant like the flame retardant resin composition of Comparative Example 5, the flame retardancy to satisfy UL-94 V-2 appears, but it can be seen that the heat deformation temperature is significantly lowered.

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

 The thermoplastic flame-retardant resin composition of the present invention does not contain a halogen-based compound, and has excellent properties of flame retardancy and mechanical properties by using an organic peroxide in a mixed resin of a rubber-modified styrene graft copolymer and a styrene copolymer.

Claims (10)

To 100 parts by weight of the base resin mixture comprising 5 to 80 parts by weight of the rubber-modified styrenic graft copolymer, and 95 to 20 parts by weight of the styrene copolymer, Thermoplastic flame retardant resin composition comprising 0.01 to 10 parts by weight of organic peroxide and 0.01 to 10 parts by weight of nanoclay. According to claim 1, wherein the rubber modified styrene-based graft copolymer Based on 100 parts by weight of the rubber-modified styrenic graft copolymer, a) 30 to 65 parts by weight of at least one styrene-based resin selected from the group consisting of styrene, alpha methyl styrene, and nuclear substituted styrene; And b) 10 to 30 parts by weight of at least one acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate c) 10 to 60 parts by weight of one or more rubbery copolymers selected from the group consisting of butadiene rubber, styrene-butadiene copolymer, isoprene rubber, and butadiene-isoprene copolymer. The method of claim 1, wherein the styrenic copolymer Per 100 parts by weight of the styrene-based copolymer, a) 50 to 90 parts by weight of at least one styrene-based resin selected from the group consisting of styrene, alpha methyl styrene, and nuclear substituted styrene; And b) 10 to 50 parts by weight of at least one acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate. The method of claim 1, wherein the organic peroxide is ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, At least one thermoplastic flame retardant resin composition selected from the group consisting of peroxy ester and peroxycarbonate. delete The thermoplastic flame retardant resin composition of claim 1, wherein the nanoclay is at least one layered silicate selected from the group consisting of montmorillonite, hectorite, vermiculite, saponite, organic layered silicates organicized thereof, or a mixture of two or more thereof. The thermoplastic flame retardant of claim 6, wherein the organic layer silicate is treated with one or more organic agents selected from the group consisting of alkylammonium, alcohols, and ketones to increase compatibility with the base resin mixture. Resin composition. The thermoplastic flame retardant resin of claim 1, wherein the thermoplastic flame retardant resin composition further comprises at least one additive selected from the group consisting of a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, an antidropping agent, a pigment, and an inorganic filler. Composition. a) with respect to 100 parts by weight of a rubber-modified styrenic graft copolymer, i) 30 to 65 parts by weight of at least one styrene-based resin selected from the group consisting of styrene, alpha methyl styrene, and nuclear substituted styrene; And ii) 10 to 30 parts by weight of at least one acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate iii) Rubber modified styrenic graft copolymers by graft polymerization of 10 to 60 parts by weight of at least one rubbery copolymer selected from the group consisting of butadiene rubber, styrene-butadiene copolymer, isoprene rubber, and butadiene-isoprene copolymer Preparing the coalescing; b) with respect to 100 parts by weight of the styrenic graft copolymer, i) 50 to 90 parts by weight of at least one styrene-based resin selected from the group consisting of styrene, alpha methyl styrene, and nuclear substituted styrene; And ii) preparing a styrene copolymer by copolymerizing 10 to 50 parts by weight of one or more acrylic resins selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate; c) preparing a basic resin mixture by mixing 5 to 80 parts by weight of the rubber-modified styrenic graft copolymer and 95 to 20 parts by weight of the styrene copolymer with respect to 100 parts by weight of the base resin mixture; And d) mixing 0.01 to 10 parts by weight of organic peroxide and 0.01 to 10 parts by weight of nanoclay with respect to 100 parts by weight of the base resin mixture Method for producing a thermoplastic flame retardant resin composition comprising a. delete