KR101683339B1 - Antidripping Agent for Styrene based Flame Resistant Resin, and Styrene Flame Resistant Resin Composition Comprising The Same - Google Patents

Abstract

The present invention relates to a styrenic flame retardant resin and a styrene flame retardant resin composition containing the styrenic flame retardant resin. The styrenic flame retardant resin composition according to the present invention provides flame retardancy, fluidity, And a styrene-based flame retardant resin composition excellent in shrinkage ratio.

Description

TECHNICAL FIELD [0001] The present invention relates to a styrenic flame retardant resin composition, and a styrene flame retardant resin composition containing the styrenic flame retardant resin composition,

The present invention relates to a styrenic flame retardant resin composition and a styrenic flame retardant resin composition containing the styrenic flame retardant resin composition. More particularly, the present invention relates to a styrenic flame retardant resin composition which is excellent in flame retardance, fluidity, And a styrene flame retardant resin composition containing the same.

The rubber-modified styrenic resin has excellent processability and physical properties and is widely used as an exterior material for electrical and electronic products and office equipment. However, the rubber-modified styrenic resin itself has a characteristic of easily burning and has little resistance to fire.

Due to these problems, rubber-modified styrene resins used in electrical and electronic products and office equipment must satisfy the flame retardant specifications in order to ensure the safety of electric and electronic products against fire.

Methods of imparting flame retardancy to a resin include a method of polymerizing a resinous material using a monomer containing a flame retardant component and a method of adding a flame retardant and a flame retarding agent to the resin to impart flame retardancy. In the latter case, flame retardancy is imparted through kneading of a halogen-based flame retardant and a non-halogen-based flame retardant. However, in the case of phosphorus-based, nitrogen-based and hydroxide-based flame retardants, which are non-halogen flame retardants, the efficiency is significantly lower than that of halogen-based flame retardants. Therefore, a high content ratio to achieve a certain level of flame retardancy is inevitable, . As a result, halogen-based flame retardants are the most effective method for simultaneously satisfying flame retardance and mechanical properties of resins, and brominated organic flame retardants are most effective for rubber-modified styrene resins.

When the flame retardancy is realized by using such a brominated organic flame retardant and a preparation, a dropping phenomenon may occur due to a decrease in viscosity due to an increase in the resin temperature during the combustion of the resin. Such a dropping phenomenon may occur in another combustion portion It can cause diffusion. Therefore, in order to realize flame retardancy of V-0 or V-1 class, an anti-drip agent is typically used, and fluorine-based fluorinated polyethylene is used as a typical anti-drip agent.

The fluorinated polyethylene-based drip inhibitor uses a phenomenon that the linear shrinkage occurs when the resin is present in the resin as a linear improvement under high temperature conditions. When the resin is contained in the resin according to such physical properties, the fluidity of the resin is lowered. It is disadvantageous in that it is difficult to process due to the phenomenon of swelling (Die swell) and single-strand phenomenon of strand.

Also, when used as an electronic part of a large-sized electronic product, shrinkage of the anti-dripping agent may affect the overall shrinkage of the resin.

Therefore, it is necessary to develop a styrene-based flame retardant resin composition using an inhibitor that exhibits an effect of preventing dropping without effectively reducing the shrinkage of the resin.

That is, the object of the present invention is to provide a flame-retardant agent capable of replacing the fluorine-containing antistatic agent to overcome the above-mentioned problems, and to provide a styrene-based flame retardant resin composition containing the same.

According to the present invention,

And a viscosity of 500,000 to 7,000,000 cSt as measured at 25 DEG C, represented by the following formula (1): < EMI ID = 1.0 >

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 1 to 20 carbon atoms.

Further, according to the present invention,

Styrene-based flame retardant resin; And a compound represented by the following general formula (1) and having a viscosity of 500,000 to 7,000,000 cSt measured at 25 캜; Based flame retardant resin composition.

[Chemical Formula 1]

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 1 to 20 carbon atoms.

According to the present invention, there is provided a styrenic flame retardant resin composition which improves fluidity and has high flame retardancy by minimizing flame retardance, flowability, and shrinkage by providing a specific antidoading agent replacing the fluorine-based antistatic agent conventionally used as the styrenic flame retardant resin It is effective.

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

In the present invention, there is a technical feature to provide an antifogging agent that can replace the fluorine-based antifogging agent as the antifogging agent for the styrene-based flame retardant.

The anti-dripping agent is characterized by comprising a compound represented by the following formula (1) and having a viscosity of 500,000 to 7,000,000 cSt measured at 25 ° C.

[Chemical Formula 1]

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 1 to 20 carbon atoms.

For example, the styrene-based flame retardant resin may include a styrenic thermoplastic resin, a bromine-based flame retardant, and an antimony-based flame retardant auxiliary.

In Formula 1, the carbon number of the alkyl group may be an integer of 4 to 18.

As a specific example, the viscosity of the compound represented by the formula (1) is in the range of 500,000 to 7,000,000 cSt or 500,000 to 5,000,000 cSt measured at 25 ° C.

Examples of the styrene-based flame retardant resin composition containing the anti-drip agent include a styrene-based flame retardant resin; And a compound represented by the following general formula (1) and having a viscosity of 500,000 to 7,000,000 cSt measured at 25 캜; . &Lt; / RTI &gt;

[Chemical Formula 1]

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 1 to 20 carbon atoms.

As a specific example, the composition may include 40 parts by weight in the brominated flame retardant 1 based on 100 parts by weight of the styrenic resin; 1 to 10 parts by weight of an antimony-based flame-retardant auxiliary, and 0.3 to 5 parts by weight of the above-mentioned antifogging agent.

The styrenic resin may be one or more of acrylonitrile-butadiene-styrene copolymer and styrene-acrylonitrile copolymer.

The styrene-based resin may be, for example, 10 to 90 wt% of an acrylonitrile-butadiene-styrene copolymer and 90 to 10 wt% of a styrene-acrylonitrile copolymer.

For example, the acrylonitrile-butadiene-styrene copolymer is prepared by emulsion graft polymerization, and a rubber content of 30 to 70% by weight can be used.

For example, the acrylonitrile-butadiene-styrene copolymer may be prepared by emulsion-graft-polymerizing butadiene rubber, acrylonitrile monomer, and styrene monomer, and then coagulating, dehydrating and drying the same, To 0.5 탆 of a butadiene rubber is contained in an amount of 30 to 70% by weight.

As another example, the emulsion graft polymerization may be carried out by using 30 to 70 parts by weight of butadiene rubber, 0.6 to 2 parts by weight of an emulsifier, 0.2 to 2 parts by weight of a molecular weight modifier, 1 to 5 parts by weight of acrylonitrile and 20 to 65 parts by weight of styrene may be continuously or batchwise added to a mixed solution containing 1 part by weight of a polymerization initiator and 0.05 to 0.5 parts by weight of a polymerization initiator.

For reference, the flocculation may be carried out by an acid, a salt, or a polymer.

For example, the styrene-acrylonitrile copolymer is prepared by bulk polymerization and has a weight average molecular weight of 50,000 to 150,000 g / mol and an acrylonitrile monomer content of 20 to 40 parts by weight, Two or more species may be used in combination.

Examples of the bromine-based flame retardant include hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenylethane, brominated (Tetrabromophthalimide), tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate, tetrabromobisphenol A bis (Allylthylene), and derivatives thereof, and the like.

The brominated organic flame retardant may be contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the styrene resin in consideration of the effect that the resin composition does not significantly decrease mechanical strength and fluidity and has excellent thermal stability and weatherability.

The antimony-based flame-retarding auxiliary acts to improve the flame retardancy by synergizing with the brominated organic flame retardant. Examples thereof include antimony trioxide and antimony pentoxide. They may be used singly or in combination of two or more kinds. , Antimony trioxide can be used.

The antimony compound may be contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the styrene-based resin so as to ensure sufficient flame retardancy without a large decrease in impact strength.

The anti-drip agent can prevent the dropping of the styrene resin during the combustion process.

The above-mentioned antifogging agent can not be expected to further increase synergistic effect of the antifogging phenomenon when used in an excessively large amount, and may be degraded in mechanical properties, and may be contained in an amount of 0.1 to 5 parts by weight, or 0.3 to 5 parts by weight, based on 100 parts by weight of the styrene- .

The composition has a V-0 standard when measured according to the UL94 method.

Also, the composition may have a molding shrinkage ratio according to ASTM D955 within the range of 0.49 to 0.50.

The composition may include at least one additive selected from an impact modifier, a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, a UV-blocking agent, a pigment and an inorganic filler, 0.1 to 20 parts by weight.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

[Example]

Preparation Example 1-3: Preparation of the compound of formula (1)

Preparation Example 1:

A polydimethylsiloxane compound of Dow Corning Company having a viscosity of 500,000 cSt as measured by ASTM D445 kinematic viscosity measurement at 25 캜 was prepared.

[Chemical Formula 1]

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 1 to 20 carbon atoms.

Production Example 2

A polydimethylsiloxane compound of Dow Coating having a viscosity of 5,000,000 cSt measured at 25 캜 was prepared.

Production Example 3

A polydimethylsiloxane compound of Dow Coat Co., Ltd., which satisfies the above formula (1) and has a viscosity of 10,000 cSt measured at 25 캜, was prepared.

Preparation Example 4: Preparation of styrene resin

38 parts by weight of an ABS copolymer having an average particle size of about 0.3 占 퐉 of butadiene rubber prepared by emulsion graft polymerization, 25 parts by weight of acrylonitrile and 25 parts by weight of styrene having a weight average molecular weight of 120,000 g / mol, - 42 parts by weight of acrylonitrile copolymer, prepared by bulk polymerization 100 parts by weight of a styrene-based resin composed of 23 parts by weight of acrylonitrile and 30 parts by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 110,000 g / mol was prepared.

Example 1: Production of styrene-based flame retardant resin

23 parts by weight of tetrabromobisphenol A, 3 parts by weight of antimony trioxide, and 0.4 part by weight of the antifoaming agent of Production Example 1 were added to 100 parts by weight of the styrene resin of Production Example 4 through a Henschel mixer, A styrene type flame retardant resin in the form of pellets was prepared through a twin screw extruder.

The prepared pellets were injection-molded to prepare specimens for physical properties and flame retardancy.

Example 2

The same procedure as in Example 1 was repeated, except that the drip inhibitor of Preparation Example 1 was replaced with the drip inhibitor of Preparation Example 2 in Example 1 above.

Example 3

The same procedure as in Example 1 was repeated except that the amount of the anti-drip agent in Production Example 1 was increased to 1.0 part by weight in Example 1.

Example 4

The same procedure as in Example 1 was repeated except that the amount of the anti-drip agent in Production Example 2 was increased to 1.0 part by weight in Example 2.

Comparative Example 1

The same procedure as in Example 1 was repeated except that 0.1 parts by weight of the anti-drip agent of Production Example 1 was added to the above Example 1.

Comparative Example 2

The same procedure as in Example 1 was repeated except that 0.2 part by weight of the anti-drip agent of Production Example 1 was added.

Comparative Example 3

The same procedure as in Example 1 was repeated except that the drip inhibitor of Preparation Example 1 was replaced with the drip inhibitor of Production Example 3 in Example 1 above.

Comparative Example 4

The same procedure as in Example 1 was repeated except that 0.1 part by weight of fluorinated polyethylene (product name of Ashahi Kasei Co., Ltd.) as a fluorine-based anti-drip agent used in Example 1 was added instead of the conventional antifogging agent .

Comparative Example 5

The same procedure as in Example 1 was repeated except that the anti-dripping agent of Production Example 1 was not added to the above-mentioned Example 1.

Comparative Example 6

The same procedure as in Comparative Example 4 was repeated except that 0.3 part by weight of the fluorinated polyethylene was added in Comparative Example 4. However, when an excess amount of fluorinated polyethylene is added in an amount of 0.2 parts by weight or more, a monofilament phenomenon occurs, causing a large problem in the extrusion processability, so that the result of the extrusion process can not be obtained.

The components and contents used in Examples 1-4 and Comparative Examples 1-5 are summarized in Table 1 below.

division Example Comparative Example One 2 3 4 One 2 3 4 5 ABS 30 30 30 30 30 30 30 30 30 SAN 70 70 70 70 70 70 70 70 70 TBBA 24 24 24 24 24 24 24 24 24 Sb2O3 4 4 4 4 4 4 4 4 4 Anti-drop agent 0.4
(Production Example 1) 0.4
(Production Example 2) 1.0
(Production Example 1) 1.0
(Production Example 2) 0.1
(Production Example 1) 0.2
(Production Example 1) 0.4
(Production Example 3) 0.1
(Fluorine) -

The physical properties of the specimens prepared in Examples 1-4 and Comparative Examples 1-5 were measured in the following manner and summarized in Table 2.

[Measurement of physical properties]

* Notched Izod Impact Strength: Specified according to ASTM D-256 using 1/8 "thick specimens.

Tensile strength : Measured according to ASTM-D638.

Melt Flow Index : Measured according to ASTM D-1238.

* Heat Distortion Temperature : Measured according to ASTM D648.

* Dropping phenomenon : Based on UL-94, it was judged that there was molten dropping phenomenon of the specimen during the burning time with or without scraping surface at the bottom of the combustion specimen.

* Vertical Flammability: Five specimens of 1/12 inch thickness were measured according to UL-94 test standards. The primary combustion and the secondary combustion time are indicated by burning if the combustion is not completed within 30 seconds, and the remaining time of the flame is indicated after 10 seconds of flame burning.

Molding shrinkage: Measured according to ASTM D955.

division Example Comparative Example One 2 3 4 One 2 3 4 5 1/8 "imp 22.5 21.2 20.1 19.2 22.0 22.4 22.5 22.4 22.6 TS 442 435 467 449 440 440 443 440 443 MI 64.0 57.2 60.2 53.2 68.2 66.0 70.2 59.7 67.4 HDT 77.9 78.5 78.3 79.1 78.2 78.4 75.3 78.1 78.0 Loading phenomenon radish radish radish radish U U U radish U Burn time (s) 3, 2
2, 2
1, 2
3, 1
2, 2 1, 2
2, 1
3, 2
2, 2
1, 1 1, 1
1, 4
2, 2
1, 2
2, 1 2, 2
1, 2
3, 2
2, 1
1, 4 6, 24 (d)
3, B / O (d)
B / O (d)
4, B / O (d)
13, 24 (d) 5, B / O (d)
9, B / O (d)
3, B / O (d)
9, B / O (d)
B / O 4, 2 (d)
2, 5 (d)
5, 9 (d)
7, 2 (d)
2, 2 1, 2
1, 1
2, 1
1, 1
2, 1 4, 17 (d)
9, 22 (d)
3, 21 (d)
5, B / O (d)
9, 17 (d) UL-94 V-0 V-0 V-0 V-0 V-2 V-2 V-2 V-0 V-2 Contraction ratio 0.50 0.49 0.50 0.50 0.49 0.50 0.49 0.56 0.48

As shown in Table 2, in Examples 1 to 4 in which the anti-drip agent was used in Production Example 1 or Production Example 2, Comparative Examples 1 and 2 in which the amount of the anti-drip agent was small, Comparative Example 3, No dripping phenomenon occurred compared with Comparative Example 5 in which no antifoaming agent was used, and a stable V-0 flame retardancy was exhibited.

Although the amount of the antifogging agent of the present invention was slightly higher than that of the conventional fluorine-based antifriction agent of Comparative Example 4, the shrinkage of the product of Comparative Examples 1 to 5 was greatly reduced.

Particularly, in Example 1 using the anti-drip agent of Production Example 1, it was confirmed that the fluidity of the anti-drip agent of Example 2 was improved without deteriorating mechanical properties.

Claims (15)

1. A drip inhibitor for styrene-based flame retardants, comprising a compound represented by the following general formula (1) and having a viscosity of 500,000 to 5,000,000 cSt measured at 25 DEG C, wherein the styrene-based flame retardant is an acrylonitrile-butadiene- Acrylonitrile copolymer, a bromine-based flame retardant, and a tetrabromobisphenol-A and an antimony-based flame retardant auxiliary.

[Chemical Formula 1]

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 4 to 18 carbon atoms. delete delete delete Styrene-based flame retardant resin; And a compound represented by the following formula (1) and having a viscosity of 500,000 to 5,000,000 cSt measured at 25 캜; 1 to 40 parts by weight of tetrabromobisphenol A as a bromine-based flame retardant based on 100 parts by weight of the styrene-based flame retardant resin; 1 to 10 parts by weight of an antimony flame retardant auxiliary, and 0.3 to 1 part by weight of the above-mentioned antifogging agent, wherein the styrene-based flame retardant resin comprises 10 to 90% by weight of an acrylonitrile-butadiene- Wherein the acrylonitrile-butadiene-styrene copolymer is prepared by emulsion graft polymerization, the rubber content is 30 to 70% by weight, and the styrene-acrylonitrile copolymer has a weight average molecular weight 50,000 to 150,000 g / mol, and the content of the acrylonitrile monomer is 20 to 40 parts by weight.
[Chemical Formula 1]

A is an integer of 0 to 50, b is an integer of 5 to 250, and 0 < a + b &lt; = 300. In the formula, R ₁ and R ₂ are independently hydrocarbons having an alkyl group having 4 to 18 carbon atoms. delete delete delete delete delete delete 6. The method of claim 5,
Wherein the antimony-based flame retardant auxiliary is at least one selected from antimony trioxide and antimony pentoxide. 6. The method of claim 5,
Wherein the composition has a V-0 standard according to UL94 method. 6. The method of claim 5,
Wherein the composition has a molding shrinkage as measured by ASTM D955 in the range of 0.49 to 0.50. 6. The method of claim 5,
Wherein the composition comprises at least one additive selected from the group consisting of an impact modifier, a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet screener, a pigment and an inorganic filler.