KR101745298B1 - Additive for inhibiting decomposition of flame retardant and thermoplastic flame retardant resin composition comprising thereof - Google Patents

Abstract

The present invention relates to an additive for suppressing flame retardant decomposition and a thermoplastic flame retardant resin composition comprising the same, wherein the benzene monocarboxylic acid and the aliphatic dicarboxylic acid And a thermoplastic flame retardant resin composition containing the thermoplastic resin and the brominated organic flame retardant in a composition comprising the thermoplastic resin and the brominated organic flame retardant.
According to the present invention, there is provided a thermoplastic flame retardant resin composition excellent in flame retardancy and excellent in thermal stability while suppressing decomposition of a brominated flame retardant by adding a specific compound capable of inhibiting thermal decomposition of a brominated organic flame retardant during injection to the thermoplastic flame retardant resin composition .

Description

TECHNICAL FIELD The present invention relates to a flame retardant decomposition inhibitor and a thermoplastic flame retardant resin composition containing the flame retardant decomposition inhibitor,

The present invention relates to a flame retardant decomposition inhibitor additive and a thermoplastic flame retardant resin composition containing the same, and more particularly, to a thermoplastic flame retardant resin composition containing at least one selected from benzene monocarboxylic acid and aliphatic dicarboxylic acid in a composition comprising a thermoplastic resin and a brominated organic flame retardant A flame retardant decomposition inhibiting additive, and a thermoplastic flame retardant resin composition containing the same.

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 mercury-free flame retardants. Examples of the flame retardant 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 relates to a thermoplastic resin composition comprising an ABS resin, a brominated organic flame retardant and an additive for suppressing decomposition of the brominated organic flame retardant, And to provide a composition.

In order to achieve the above object, the present invention provides a flame retardant decomposition inhibitor which is an additive to a composition comprising a thermoplastic resin and a brominated organic flame retardant, and which comprises at least one selected from benzene monocarboxylic acid and aliphatic dicarboxylic acid For example.

The present invention also provides a thermoplastic flame retardant resin composition comprising a thermoplastic resin, a brominated organic flame retardant, and the above-described additives, wherein the additive inhibits decomposition of the brominated organic flame retardant during the injection process do.

Hereinafter, the present invention will be described in detail.

The flame retardant decomposition inhibiting additive of the present invention is characterized by containing at least one selected from benzene monocarboxylic acid and aliphatic dicarboxylic acid as an additive to a composition comprising a thermoplastic resin and a brominated organic flame retardant.

The term "additive for suppressing flame retardant decomposition " used herein refers to an additive that inhibits 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, the benzene monocarboxylic acid and aliphatic dicarboxylic acid specified in the present invention as an additive for suppressing flame retardant decomposition include a carboxyl group capable of generating hydrogen cations, as described in the following examples, so that pyrolysis of the brominated organic flame retardant And the like.

The benzene monocarboxylic acid may be at least one selected from benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, hydroxybenzoic acid and tertiarybutylbenzoic acid, The carboxylic acid may also be at least one selected from maleic acid, fumaric acid, citraconic acid, and itaconic acid, though not limited thereto.

When a mixture of two kinds of benzene monocarboxylic acid and aliphatic dicarboxylic acid is used as an additive for suppressing flame retardant decomposition in the present invention, the blending ratio is 1: 99 to 99: 1, or 10: 90 to 90: .

In the present invention, the thermoplastic resin to which the additive is applied is not limited thereto, but it is preferable that A) 10 to 90 parts by weight of an acrylonitrile-butadiene-styrene copolymer and B) 90 to 10 parts of a styrene-acrylonitrile copolymer Parts by weight.

Specifically, the additive is added in an amount of 0.1 to 1 part by weight, specifically 0.1 to 0.5 part by weight, based on 100 parts by weight of the thermoplastic resin Is preferable because it can impart excellent thermal stability.

In addition, the brominated organic flame retardants that inhibit decomposition of the additive of the present invention include, but are not limited to, hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide , Octabromodiphenyl oxide, decabromodiphenylethane, ethylenebis (tetrabromophthalimide), tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris ) Cyanurate, tetrabromobisphenol A bis (allyl ether), and mixtures thereof.

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

As described above, the thermoplastic flame retardant resin composition providing the specific additive in combination with the thermoplastic resin and the brominated organic flame retardant in the present invention can effectively suppress the decomposition of the brominated organic flame retardant in the injection process by the additive, It is possible to obtain an injection-molded product having improved thermal stability.

The thermoplastic resin may be composed of 10 to 90 parts by weight of the acrylonitrile-butadiene-styrene copolymer and 90 to 10 parts by weight of the styrene-acrylonitrile copolymer.

The acrylonitrile-butadiene-styrene copolymer may be prepared by emulsion graft-polymerizing a butadiene rubber, an acrylonitrile monomer and a styrene monomer, followed by aggregating, It may be one which has been dried and made into a powder state.

The butadiene rubber contained in the acrylonitrile-butadiene-styrene copolymer is preferably 50 to 70% by weight of butadiene-based rubber having an average particle diameter of 0.1 to 0.5 탆 (micrometer), and 100% by weight of all monomers constituting the copolymer , 0.6 to 2 parts by weight of an emulsifier, 0.2 to 1 part by weight of a molecular weight modifier and 0.05 to 0.5 part by weight of a polymerization initiator, in an amount of 5 to 40 parts by weight of an acrylonitrile monomer and 20 to 65 parts by weight of a styrene monomer The monomer mixture may be continuously or batch-wise emulsified and graft-polymerized, followed by agglomeration with an aqueous solution of 5% sulfuric acid, dehydration and drying to obtain a powder.

The inorganic acid may be at least one member selected from sulfuric acid, hydrochloric acid and nitric acid. When the content of the butadiene rubber is less than 50% by weight, the impact resistance largely deteriorates. When the content exceeds 70% by weight, The hardness of the surface is lowered.

The styrene-acrylonitrile-based copolymer (B) is not limited to this, but it preferably contains 20 to 40% by weight of acrylonitrile-based monomer and has a weight average molecular weight (Mw) of 50,000 to 150,000 g / mol And may be used singly or in combination of two or more.

Examples of the brominated organic flame retardant that can be used in the present invention include, but are not limited to, hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide, (Triphenylphosphine) cyanurate, triphenylphosphine oxide, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, Tetrabromobisphenol A bis (allyl ether) and derivatives thereof, and most preferably tris (tribromobenzyl) cyanurate having the following formula (1).

[Chemical Formula 1]

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, according to the present invention, by adding a specific compound capable of inhibiting thermally decomposing the brominated organic flame retardant agent during injection to the thermoplastic flame retardant resin composition, it is possible to suppress degradation of the brominated flame retardant agent while controlling the thermoplasticity There is an effect of providing a flame retardant resin composition.

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 invention as set forth in the appended claims. Variations and modifications are intended to fall 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 an average particle diameter of 0.3 탆, an acrylonitrile content of 25% And 80 parts by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000, 30 parts by weight of tris (tribromobiphenyl) cyanurate (product name SR245), which is a bromine-based organic flame retardant, as an aromatic carboxylic acid And 0.1 part by weight of benzoic acid were added and uniformly 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 benzoic acid was used in Example 1.

Example  3

The procedure of Example 1 was repeated, except that fumaric acid, an aliphatic dicarboxylic acid, was used in place of benzoic acid in Example 1.

Example  4

The procedure of Example 2 was repeated except that fumaric acid was used in place of benzoic acid in Example 2.

Comparative Example  One

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

Comparative Example  2

The procedure of Example 2 was repeated, except that benzophenone represented by the following formula 3 was used instead of benzoic acid in Example 2.

(3)

Comparative Example  3

The procedure of Example 4 was repeated except that maleic anhydride of Formula 4 was used instead of fumaric acid in Example 4.

[Chemical Formula 4]

[ Test Example  One]

The properties of the thermoplastic resin composition specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 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 4 One 2 3 Emulsion Polymerization ABS 20 20 20 20 20 20 20 SAN 80 80 80 80 80 80 80 Bromine series
Organic flame retardant 30 30 30 30 30 30 30 Benzoic acid 0.1 0.5 Fumaric acid 0.1 0.5 Benzophenone 0.5 Maleic anhydride 0.5 Flammability (1/10 ")
Standard: V-1 Pass Pass Pass Pass Pass Pass Pass Surface gas generation rate after injection 2 One 2 2 5 5 6

As shown in Table 1, in Examples 1 and 2 in which tris (tribromobenzyl) cyanurate, which is a bromine-based flame retardant, and benzoic acid were simultaneously charged, in Examples 3 and 4 in which fumaric acid was added in place of benzoic acid, flame retardancy V -1, it was confirmed that the amount of gas generated during the retention test was small.

On the other hand, in Comparative Example 1 in which only the brominated organic flame retardant was added without adding benzoic acid, 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, Relative to that of the gas produced from the surface of the injection.

On the other hand, in Comparative Example 2 in which benzophenone having a chemical structure similar to that of benzoic acid but having no carboxyl group and substituted with a phenyl group was added, the flame retardancy passed through V-1, but the amount of gas generated during the retention test was larger than in Example 2 And was similar to that of Comparative Example 1.

Also, in Comparative Example 3 in which maleic anhydride having a molecular weight similar to that of fumaric acid but having no carboxyl group was added, the flame retardancy also passed through V-1, but the amount of gas generated during the retention test was larger than in Example 4, , And 2, respectively.

From the above experimental results, it can be confirmed that the heat stability is superior in all of Examples 1 to 4 in which benzoic acid or fumaric acid is added. In conclusion, it was confirmed that the thermoplastic resin composition of the present invention has excellent flame retardancy by using both the bromine-based flame retardant and the bromine flame retarder decomposition inhibitor simultaneously to improve the thermal stability and to suppress the decomposition of the flame retardant.

Claims (12)

Characterized in that at least one selected from benzoic acid and fumaric acid is contained in an amount of 0.1 to less than 0.5 parts by weight based on 100 parts by weight of the thermoplastic resin as an additive for a composition comprising a thermoplastic resin and a brominated organic flame retardant, Inhibitor additive. The method according to claim 1,
Wherein the benzoic acid and the fumaric acid are blended in a weight ratio of 1: 99 to 99: 1. The method according to claim 1,
Wherein the thermoplastic resin is composed of (A) 10 to 90 parts by weight of an acrylonitrile-butadiene-styrene copolymer, and (B) 90 to 10 parts by weight of a styrene-acrylonitrile copolymer. additive. 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 Tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate, tetrabromobisphenol A bis (allyl ether) And is contained within a range of 10 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin. A thermoplastic flame retardant resin composition comprising a thermoplastic resin, a brominated organic flame retardant, and an additive according to any one of claims 1 to 3, wherein the additive inhibits decomposition of the brominated organic flame retardant during the injection process. 6. The method of claim 5,
Wherein the thermoplastic resin comprises 10 to 90 parts by weight of the A) acrylonitrile-butadiene-styrene copolymer, and B) 90 to 10 parts by weight of the styrene-acrylonitrile copolymer. . The method according to claim 6,
Wherein the A) acrylonitrile-butadiene-styrene copolymer is a powder obtained by coagulating an emulsified graft-polymerized latex comprising 50 to 70% by weight of a diene rubber having an average particle size of 0.1 to 0.5 탆 with inorganic acid , A thermoplastic flame retardant resin composition. 8. The method of claim 7,
Wherein the inorganic acid is selected from sulfuric acid, hydrochloric acid or nitric acid. The method according to claim 6,
Wherein the styrene-acrylonitrile copolymer (B) comprises 20 to 40% by weight of an acrylonitrile monomer and has a weight average molecular weight (Mw) of 50,000 to 150,000 g / mol. 6. The method of claim 5,
The brominated organic flame retardant may be at least one selected from the group consisting of hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenylethane, ethylenebis Tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate, tetrabromobisphenol A bis (allyl ether) And is contained in a range of 10 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin. 11. The method of claim 10,
Wherein the brominated organic flame retardant is a compound represented by the following formula (1).
[Chemical Formula 1]

6. The method of claim 5,
Wherein the composition further 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 screening agent, a pigment and an inorganic filler.