KR20140066811A - Thermoplastic flame retardant resin composition and injection mold - Google Patents

Abstract

The present invention relates to a thermoplastic flame retardant resin composition and an injection mold obtained therefrom. Provided are a thermoplastic flame retardant resin composition composed of a thermoplastic resin, a bromine organic flame retardant agent and a degradation inhibitor thereof and an injection mold having superb flame retardance and heat stability obtained therefrom.

Description

TECHNICAL FIELD The present invention relates to a thermoplastic flame retardant resin composition, and a thermoplastic flame retardant resin composition and injection mold,

More particularly, the present invention relates to a thermoplastic flame retardant resin composition containing pentaerythritol as a decomposition inhibitor of a brominated organic flame retardant, and to a flame retardant resin composition containing the flame retardant and heat stability And relates to such an excellent injection-molded article.

Generally, acrylonitrile-butadiene-styrene (ABS) resins are widely used as exterior materials for electrical and electronic products and office equipment due to stiffness and chemical resistance of acrylonitrile, processability and mechanical strength of butadiene and styrene have. However, ABS resin itself has characteristics that can easily burn, and has little resistance to fire.

Due to these problems, ABS resin used in electric and electronic products and office equipment should meet the flame retardant standards to ensure the safety of electric and electronic products against fire.

The flame retardant may be added to the rubber-modified styrenic resin to prepare a rubber-modified styrenic resin. The flame retardant may be a halogen-based flame retardant, Halogen-based flame retardants such as phosphorus-based, nitrogen-based, and hydroxyl-based flame retardants. Examples of the flame retarding additives include organic acids, silicon compounds, and zinc compounds.

Since the halogen-based flame retardant has a higher flame retardancy than the non-halogen-based flame retardant and can maintain the mechanical properties of the rubber-modified styrene-based resin, a method of using a halogen bethane flame retardant And a double-brominated flame retardant is particularly effective.

However, when the ABS resin is processed by injecting the brominated flame retardant, the thermal stability is lowered due to the high temperature and pressure generated during the process, and the brominated flame retardant is decomposed and the content of the flame retardant in the resin is decreased to weaken the flame retardancy And most of all, the decomposition component of the brominated flame retardant causes deterioration of appearance quality and physical properties of products such as discoloration. Further, the decomposition component of the brominated flame retardant may adversely affect the working environment and the human body.

This can be solved by improving the thermal stability of the resin and suppressing decomposition of the brominated flame retardant. Therefore, development of an ABS resin having excellent flame retardancy and excellent thermal stability is still required.

In order to solve the problems of the prior art described above, the present invention provides a thermoplastic flame retardant resin composition comprising a thermoplastic resin containing an ABS resin, a brominated organic flame retardant and a specific compound for inhibiting decomposition of the brominated organic flame retardant, It is an object of the present invention to provide an injection molded article.

In order to achieve the above object, the present invention provides a thermosetting resin composition comprising a thermoplastic resin, a brominated organic flame retardant and a decomposition inhibitor thereof,

The decomposition inhibitor may be used in an amount of 0.1 to 2.9 parts by weight based on 100 parts by weight of the thermoplastic resin Within range And a thermoplastic flame retardant resin composition.

Further, the present invention provides an injection molded article obtained by the thermoplastic resin composition.

Hereinafter, the present invention will be described in detail.

The thermoplastic flame retardant resin composition excellent in thermal stability of the present invention is characterized by comprising a thermoplastic resin, a brominated organic flame retardant and a decomposition inhibitor thereof.

The term " inhibitor for decomposition of brominated organic flame retardant " used herein refers to an additive for inhibiting the decomposition of the brominated organic flame retardant contained in the composition in the injection step of the thermoplastic resin composition provided in the present invention. For reference, thermal stability in the present invention is achieved by suppressing the decomposition of the brominated organic flame retardant contained in the composition in the injection step of the thermoplastic resin composition which provides the thermoplastic resin composition. For reference, pentaerythritol presented as a decomposition inhibitor in the present invention has four hydrogen cations generated by retaining four hydroxyl groups in one molecule, as shown in the following examples, and these cations suppress the pyrolysis of the brominated organic flame retardant As shown in Fig.

The thermoplastic resin to which the above-described decomposition inhibitor is applied is not limited to the above, but it is preferable that A) 10 to 90 parts by weight of an acrylonitrile-butadiene-styrenic copolymer and B) a styrene-acrylonitrile copolymer 90 To 10 parts by weight. For example, 20 to 80 parts by weight of an acrylonitrile-butadiene-styrene copolymer and 80 to 20 parts by weight of a styrene-acrylonitrile copolymer, or A) acrylonitrile -Butadiene-styrene copolymer, and B) 80 to 40 parts by weight of styrene-acrylonitrile-based copolymer.

The decomposition inhibitor may be added in an amount of 0.1 to 2.9 parts by weight, 0.1 to 1 part by weight, Or 0.1 to 0.5 parts by weight Is preferable because it can impart excellent thermal stability.

The acrylonitrile-butadiene-styrenic copolymer may be prepared by emulsion-graft-polymerizing butadiene-based rubber, acrylonitrile-based monomer and styrene-based monomer, and then agglomerating it into sulfuric acid, It may be one which has been dried and made into a powder state.

The butadiene rubber contained in the acrylonitrile-butadiene-styrene copolymer preferably has a number average particle diameter of 0.5 micrometer or less, or 0.1 to 0.5 占 퐉 butadiene rubber of 50 to 70 weight% 5 to 40 parts by weight of an acrylonitrile monomer and 5 to 40 parts by weight of an acrylonitrile monomer are added to a mixed solution comprising 0.6 to 2 parts by weight of an emulsifier, 0.2 to 1 part by weight of a molecular weight adjuster and 0.05 to 0.5 part by weight of a polymerization initiator, 20 to 65 parts by weight of a monomer mixture may be continuously or batchwise emulsified and emulsion graft-polymerized, followed by agglomeration, dehydration and drying in an aqueous 5% sulfuric acid solution.

For reference, the thermoplastic resin has excellent impact resistance and surface hardness within the range of the butadiene rubber, for example, the butadiene rubber may be in the range of 50 to 60% by weight.

The styrene-acrylonitrile-based copolymer (B) is not limited to the above-mentioned styrene-acrylonitrile copolymer, but it may contain 20 to 40% by weight or 20 to 30% by weight of the acrylonitrile monomer in the copolymer, Mw) of from 50,000 to 150,000 g / mol, or from 60,000 to 150,000 g / mol, may be used singly or in combination of two or more.

The brominated organic flame retardant may be, for example, but not limited to, hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide, octabromodiphenyloxide , Tribromodiphenyl ether, ethylenebis (tetrabromophthalimide), tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate, tetra Bromobisphenol A bis (allyl ether) and derivatives thereof, and most preferably tris (tribromobiphenyl) cyanurate having the following formula (1) or brominated epoxy oligomer having the following formula (2).

[Chemical Formula 1]

(2)

The content of the brominated organic flame retardant is 10 to 40 parts by weight, or 20 to 30 parts by weight, based on 100 parts by weight of the thermoplastic resin , And the thermoplastic resin composition produced within this range does not deteriorate mechanical strength and fluidity, and has an excellent heat resistance and weather resistance.

Further, the composition of the present invention may further comprise at least one additive selected from the group consisting of an impact modifier, a lubricant, a heat stabilizer, an antistatic agent, an antioxidant, a light stabilizer, a UV light stabilizer, a pigment and an inorganic filler.

As described above, the thermoplastic flame retardant resin composition providing the thermoplastic resin, the brominated organic flame retardant and the decomposition inhibitor thereof in combination in the present invention can effectively decompose the brominated organic flame retardant generated mainly during the injection process by the additive An injection molded article having excellent flame retardancy and excellent thermal stability can be obtained.

As described above, according to the thermoplastic flame retardant resin composition of the present invention, the brominated organic flame retardant effectively suppresses pyrolysis, which is mainly generated during the injection process, and provides an injection molded article excellent in flame retardancy and excellent in thermal stability.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  One

 20 parts by weight of an ABS copolymer (product name: DP270-butadiene rubber 55% by weight, manufactured by LG Chemical Co., Ltd.) prepared by emulsion graft polymerization using a butadiene rubber latex having a number average particle diameter of 0.3 탆, 20 parts by weight of acrylonitrile And 80 parts by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 were added 30 parts by weight of tris (tribromophenyl) cyanurate (product name SR245) as a brominated organic flame retardant, 30 parts by weight of pentaerythritol And 0.1 part by weight were added. The mixture was homogeneously mixed using a Henschel mixer, and then a thermoplastic resin composition in the form of a pellet was produced through a twin-screw extruder.

The pelletized thermoplastic resin composition was injection-molded into specimens for physical properties and flame retardancy.

Example  2

The procedure of Example 1 was repeated except that 0.5 parts by weight of pentaerythritol was used in Example 1.

Example  3

The procedure of Example 1 was repeated except that 1.0 part by weight of pentaerythritol was used in Example 1.

Comparative Example  One

The procedure of Example 1 was repeated except that pentaerythritol was not added in Example 1.

Comparative Example  2

The procedure of Example 2 was repeated, except that 1-octanol was added instead of pentaerythritol.

Comparative Example  3

The procedure of Example 2 was repeated, except that methanol was used instead of pentaerythritol.

Comparative Example  4

The same experiment was repeated except that 3 parts by weight of pentaerythritol was added in Example 1.

Comparative Example  5

The same experiment was repeated except that 0.05 parts by weight of pentaerythritol was added in Example 1.

[ Test Example  One]

The properties of the thermoplastic resin composition specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were measured by the following methods, and the results are shown in Table 1 below.

* Vertical Flammability: Measured according to UL-94.

* Comparison test of surface gas generation after retention: In all commonly used injection molding machines, the resin was injected for 15 minutes at high temperature (250 ° C or higher) inside the nozzle of the injection machine to induce pyrolysis of the resin composition and proceeded with injection. After evaluating the number of gas generating elements on the outer surface of the article to be inspected, the degree of gas generation was the lowest and the degree of excellent thermal stability was rated as 0, and the degree of gas generation was the lowest.

division Example Comparative Example One 2 3 One 2 3 4 5 Emulsion Polymerization ABS 20 20 20 20 20 20 20 20 SAN 80 80 80 80 80 80 80 80 Brominated organic flame retardant 30 30 30 30 30 30 30 30 Pentaerythritol 0.1 0.5 1.0 3.0 0.05 n-octanol 0.5 Methanol 0.5 Flammability (1/10 "), standard: V-1 Pass Pass Pass Pass Pass Pass Fail Pass Surface gas generation rate after injection 2 2 3 5 6 5 7 5

As shown in Table 1, in Examples 1, 2 and 3 in which tris (tribromophenyl) cyanurate, which is a bromine-based flame retardant, and pentaerythritol were simultaneously charged, flame retardancy V- And it was confirmed that the amount of generation was small.

On the other hand, in Comparative Example 1 in which only the brominated organic flame retardant was added without pentaerythritol, the flame retardancy passed through V-1, but the degree of decomposition of the flame retardant was high at the high temperature condition in the retention test, , 2, which are relatively large compared to those of the gas generating station identified on the surface of the injection molding.

On the other hand, in Comparative Example 2 in which the compound of Formula 4 (molecular weight: 130.23) having a molecular weight similar to that of pentaerythritol (molecular weight: 136.15) was added but only one hydroxyl group was added, the flame retardancy passed through V-1, Was higher than that of Example 2 and was similar to that of Comparative Example 1.

Also, in Comparative Example 3 in which methanol having a molecular weight of 1/4 of that of pentaerythritol (molecular weight: 136.15) was added and only one hydroxyl group was added, the flame retardancy also passed through V-1, Was greater than that of Example 2 and was similar to that of Comparative Examples 1 and 2.

On the other hand, in the case of Comparative Example 4 in which 3 parts by weight of pentaerythritol was added in an excess amount than Example 3, it was confirmed that the amount of gas generated during the retention test was large and the flame retardancy did not pass through V-1. In addition, in the case of Comparative Example 5 in which 0.05 parts by weight of pentaerythritol was added in a small amount compared with Example 1, the effect of suppressing the gas generation amount during the retention test was not sufficiently exhibited because the amount of the pentaerythritol was too small. Respectively.

From the above experimental results, it can be confirmed that the thermal stability is superior in Examples 1, 2 and 3 in which pentaerythritol was added.

In conclusion, it was confirmed that the thermoplastic resin composition of the present invention has excellent flame retardancy by using the bromine-based flame retardant and pentaerythritol as the decomposition inhibitor thereof in combination to improve the thermal stability and to suppress the decomposition of the flame retardant.

Claims (10)

A thermoplastic resin, a brominated organic flame retardant and a decomposition inhibitor thereof,
The decomposition inhibitor may be used in an amount of 0.1 to 2.9 parts by weight based on 100 parts by weight of the thermoplastic resin Within range Based on the weight of the thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the decomposition inhibitor is pentaerythritol. The method according to claim 1,
Wherein the brominated organic flame retardant is 10 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin. The method according to claim 1,
Wherein the thermoplastic resin is composed of 10 to 90 parts by weight of an acrylonitrile-butadiene-styrene copolymer and 90 to 10 parts by weight of a styrene-acrylonitrile copolymer, By weight based on the total weight of the thermoplastic flame retardant resin composition. 5. The method of claim 4,
Wherein the A) acrylonitrile-butadiene-styrenic copolymer is a powder obtained by agglomeration of an emulsified graft-polymerized latex comprising 50 to 70% by weight of a diene rubber having a number average particle diameter of 0.1 to 0.5 μm Thermoplastic flame retardant resin composition. 5. The method of claim 4,
Wherein the styrene-acrylonitrile copolymer (B) comprises acrylonitrile monomer in the copolymer in an amount of 20 to 40% by weight and has a weight average molecular weight (Mw) of 50,000 to 150,000 g / mol. Flame retardant resin composition. The method according to claim 1,
The brominated organic flame retardant may be at least one selected from the group consisting of hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenylethane, ethylenebis Selected from tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate, and tetrabromobisphenol A bis (allyl ether) And at least one thermoplastic flame retardant resin composition. 8. The method of claim 7,
Wherein the brominated organic flame retardant is at least one compound represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

The method according to claim 1,
Wherein the composition comprises at least one additive selected from the group consisting of an impact modifier, a lubricant, a heat stabilizer, an antistatic agent, an antioxidant, a light stabilizer, an ultraviolet screener, a pigment and an inorganic filler. An injection-molded article obtained by the thermoplastic resin composition according to any one of claims 1 to 9.