KR101140516B1 - Thermoplastic flame retardant resin composition - Google Patents

Abstract

The present invention is a base resin consisting of 9 to 80% by weight of a rubber-modified styrene compound-containing graft copolymer, 19 to 90% by weight styrene-based compound-containing copolymer, and 1 to 30% by weight of an epoxy resin having a structure of Formula 1 And it relates to a thermoplastic flame-retardant resin composition comprising 1 to 30 parts by weight of a phosphite compound having a structure of formula (2) relative to 100 parts by weight of the base resin.

According to the present invention, not only has the effect of providing a thermoplastic flame-retardant resin composition excellent in flame retardancy but also excellent in impact strength and heat resistance, and by using an epoxy resin as a char forming agent, a white index compared to a flame retardant resin using a phenol resin as a char forming agent. High index) and low yellowness index (Yellowness Index) is easy to implement a white color, there is an effect of providing a flame retardant resin composition excellent in weatherability.

[Formula 1]

In Chemical Formula 1,

n is from 1 to 10000,

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₃ are an alkyl group or an aryl group.

Thermoplastic flame retardant resin composition, rubber modified styrene compound containing graft, styrene compound containing copolymer, epoxy resin, phosphite compound, flame retardancy, impact strength, heat resistance, weather resistance, white index, yellow index

Description

Thermoplastic flame retardant composition {THERMOPLASTIC FLAME RETARDANT RESIN COMPOSITION}

The present invention relates to a thermoplastic flame retardant resin composition, and more particularly, to a thermoplastic flame retardant resin composition having excellent flame retardancy, impact strength and heat resistance, and easy to implement white color and excellent weather resistance.

Rubber-modified styrene resins have excellent processability and excellent physical and cosmetic properties such as impact strength, and are widely used in electrical and electronic products and office equipment. Such electrical and electronic products and office equipment have a risk of fire, and studies to impart flame retardancy to rubber-modified styrene resins have been continuously conducted.

It is known to use a halogen compound as a conventional flame retardant applied to a resin composition as the most effective method. However, since halogen-based compounds generate gases that corrode molds during molding of resins, and emit toxic gases that are harmful to humans during combustion, they are subject to restrictions due to tightening environmental regulations.

Accordingly, much attention has been focused on providing flame retardancy to rubber-modified styrene resins without using halogen compounds as flame retardants, and rubber-modified styrene flame-retardant resin compositions prepared by using phosphate-based compounds as flame retardants It is widely used in office equipment, such as a printer.

However, since the phosphate ester compound used as a flame retardant has a low melting point and is easily decomposed at the processing temperature of the resin, a resin composition using the same may cause pyrolysis gas and mold deposit phenomenon during long processing, resulting in poor appearance of the product. There is this.

In order to overcome this problem, Japanese Patent Application Laid-Open No. 5-1079 discloses a flame retardant having a diphosphate ester structure having an aromatic phenyl group as a linkage to improve the volatility problem of the phosphate ester compound. 043769 discloses a flame retardant having a structure in which a substituent having 12 to 25 carbon atoms is introduced into a phenyl group. However, the above conventional technologies have a problem in that heat resistance and mechanical properties are degraded.

On the other hand, rubber-modified styrene-based resins, particularly acrylonitrile-butadiene-styrene copolymer resins (hereinafter referred to as ABS resins) have a disadvantage in that it is difficult to expect a flame retardant effect in a solid phase because there is little char remaining during combustion. Therefore, it is necessary to further add a char forming agent to obtain the desired flame retardancy of the rubber-modified styrene resin. In general, phenolic resins are mainly used as char forming agents.

Japanese Patent Application Laid-Open No. 7-48491 also used a phenol resin as a char forming agent in a thermoplastic copolymer resin, and phosphoric acid ester was added as a flame retardant. However, the phenolic resin has a disadvantage in that the yellow index is greatly increased due to oxidation, and the yellow index is greatly decreased, and the white index is greatly reduced, so that the color of the white color is not only difficult, but also the weather resistance is greatly reduced.

In Korean Patent Laid-Open Publication No. 10-2005-0030649, a crosslinking agent is added to the rubber-modified styrene-based resin in order to minimize the addition of a phenol resin for generation of char when burning, to increase flame retardancy and to improve heat resistance and mechanical properties. However, crosslinking causes problems in processability and recycling, and shows a significant drop in impact strength in physical properties.

Therefore, in order to overcome the problems described above, the present inventors add an epoxy resin having better weather resistance without a yellowing phenomenon to the rubber-modified styrene-based resin in place of the phenol resin as a char forming agent, and a force widely known as a conventional stabilizer. The addition of a pit compound led to the development of a resin composition with significantly improved flame resistance, impact resistance and heat resistance.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic flame-retardant resin composition excellent in flame retardancy, impact resistance and heat resistance while having excellent weather resistance without yellowing caused by oxidation.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention

Basic resin consisting of 9 to 80% by weight of rubber-modified styrene compound-containing graft copolymer, 19 to 90% by weight of styrene-based compound containing copolymer, and 1 to 30% by weight of epoxy resin having the structure

It provides a thermoplastic flame-retardant resin composition comprising 1 to 30 parts by weight of a phosphite compound having a structure of Formula 2 with respect to 100 parts by weight of the base resin.

[Formula 1]

In Chemical Formula 1,

n is from 1 to 10000,

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₃ are an alkyl group or an aryl group.

At this time, the phosphite compound is characterized in that the triaryl phosphite (triaryl phosphite) substituted with an alkyl group.

According to the present invention, not only the effect of providing a thermoplastic flame retardant resin composition excellent in flame retardancy, impact resistance and heat resistance, but also to provide a flame retardant resin composition which is easier to realize a white color and excellent weatherability than a flame retardant resin using a phenol resin as a char forming agent. It works.

Hereinafter, the present invention will be described in detail.

The thermoplastic flame-retardant resin composition according to the present invention is 9 to 80% by weight of the rubber-modified styrene compound-containing graft copolymer, 19 to 90% by weight of the styrene compound-containing copolymer, and 1 to 30 epoxy resin having a structure of the formula Base resin composed of weight percent

100 parts by weight of the basic resin, characterized in that it comprises 1 to 30 parts by weight of a phosphite (phosphite) compound having a structure of the formula (2).

[Formula 1]

In Chemical Formula 1,

n is from 1 to 10000,

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₃ are an alkyl group or an aryl group.

The rubber-modified styrene compound-containing graft copolymer according to the present invention is prepared by graft copolymerization of 10 to 60% by weight of the rubber component with 30 to 65% by weight of the styrene compound and 10 to 30% by weight of the acrylic compound.

As said rubber component, a polybutadiene, a styrene-butadiene copolymer, a polyisoprene, butadiene-isoprene copolymer, etc. can be used individually or in mixture of 2 or more types.

As the styrene compound, styrene, alphamethyl styrene, nuclear substituted styrene, or the like may be used alone or in combination of two or more thereof.

As said acryl-type compound, acrylonitrile, methyl methacrylate, butyl acrylate, etc. can be used individually or in mixture of 2 or more types.

Examples of the rubber-modified styrene compound-containing graft copolymers include acrylonitrile-butadiene-styrene (ABS) graft copolymers, acrylonitrile-ethylenepropylene rubber-styrene (AES) graft copolymers, and acrylonitrile -Acrylic rubber-styrene (AAS) graft copolymers.

The rubber-modified styrene compound-containing graft copolymer is preferably included in 9 to 80% by weight in 100% by weight of the base resin. When included in the content is excellent mechanical strength, such as impact resistance.

The styrene compound-containing copolymer according to the present invention is preferably prepared by copolymerizing 50 to 80% by weight of the styrene compound and 20 to 50% by weight of the acrylic compound.

The styrene-based compound may be used singly or in mixture of two or more kinds of styrene, alphamethyl styrene, or nuclear substituted styrene, and the like, and the acryl-based compound may be acrylonitrile, methyl methacrylate or butyl acrylate alone or two kinds. It can mix and use the above.

The styrene-based compound-containing copolymer is preferably included in 19 to 90% by weight 100% by weight of the base resin. When included in the content is excellent mechanical strength and dimensional stability, such as impact resistance.

The rubber-modified styrenic compound-containing graft copolymer and the styrene-based compound-containing copolymer may be prepared by a conventional polymerization method, and are preferably prepared by bulk polymerization or emulsion polymerization.

The epoxy resin according to the present invention is added to impart a char forming ability to the base resin, and is represented by the following Chemical Formula 1.

[Formula 1]

The epoxy resin used in the present invention may be named novolac epoxy, novolac epoxy, epoxy novolac, phenol novolac epoxy, cresol novolac epoxy or the like.

The epoxy resin according to the present invention is prepared by reacting epichlorohydrin with a phenol (or cresol) novolak resin, and its reactivity is very high, so that almost 100% of the epoxy resin compound can be obtained. The epoxy resin used in the present invention uses a commercially available product, LER N695, manufactured by Bakelite Korea.

In Formula 1, n is 1 to 10000, and 1 to 300 is preferable in consideration of mechanical properties and workability.

The epoxy resin may be used alone or in a mixture, and may be used 1 to 30% by weight based on 100% by weight of the base resin.

The phosphite compound according to the present invention has a structure of the following Chemical Formula 2, and imparts flame retardancy, heat resistance, and impact resistance to the base resin.

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₃ represent an alkyl group or an aryl group.

More specifically, the phosphite compound includes trialkyl phosphite such as trimethyl phosphite, triethyl phosphite, triisodecyl phosphite, and the like; Phosphite compounds such as trisnonylphenyl phosphite, isodecyldiphenyl phosphite, and diisodecylphenyl phosphite; Or triaryl phosphite (triaryl phosphite) etc. can be used individually or in mixture of 2 or more types.

In this case, the trialkyl phosphite may have an alkyl group having 1 to 10 carbon atoms, and the triaryl phosphite may have a phenyl group or an aryl substituted with 1 to 3 alkyl groups having 1 to 18 carbon atoms. It may have a group.

Among the phosphite compounds, triaryl phosphite may be preferably used, and more preferably triaryl phosphite substituted with an alkyl group may be used.

The phosphite compound may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin. More preferably, it may be included in 5 to 18 parts by weight, in which case it is excellent in impact resistance while maintaining flame retardancy.

The thermoplastic flame-retardant resin composition comprising the above components may further include one or more additives selected from lubricants, thermal stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers, depending on the use.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[Example]

Example  One

1. Basic resin manufacturing

As the rubber-modified styrene compound-containing graft copolymer, acrylonitrile-butadiene-styrene graft copolymer prepared by graft copolymerization of 50% by weight of butadiene rubber, 36% by weight of styrene and 14% by weight of acrylonitrile by emulsion polymerization Used.

As the styrene compound-containing copolymer, a styrene-acrylonitrile copolymer prepared by copolymerizing 73% by weight of styrene and 27% by weight of acrylonitrile by emulsion polymerization was used.

2. Preparation of thermoplastic flame retardant resin composition

100% by weight of base resin consisting of 20% by weight of acrylonitrile-butadiene-styrene graft copolymer, 65% by weight of styrene-acrylonitrile copolymer, and 15% by weight of cresol novolak epoxy resin (product of LER N695 from Bakelite Korea). 5 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals) represented by the following formula (3) as a phosphite compound was added to the part, mixed in a Henschel mixer, and then a twin screw extruder. Extruded in a temperature range of 200 ~ 240 ℃ to prepare a pellet.

(3)

Example  2

In Example 1, 12 parts by weight of a tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals), a phosphite compound, was used as the flame retardant, except that It was carried out by the method.

Example  3

Except that in Example 1 15 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals) as a flame retardant was used in the same manner as in Example 1 Was

Comparative example  One

The same method as in Example 1 was performed except that the phosphite compound, which is a flame retardant, was not used in Example 1.

Comparative example  2

In Example 1, 15 parts by weight of triphenyl phosphate (manufactured by Nippon Shopal Chemical Co., Ltd.), a phosphate ester compound, was used instead of the phosphite compound as a flame retardant. .

Comparative example  3

In Example 1, 15 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals), a phosphite compound, was used as a flame retardant, and a phenol resin was used instead of cresol novolac epoxy as a char forming agent. The same procedure as in Example 1 was carried out except for use.

 [Test Example]

The thermoplastic flame retardant resin composition pellets prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were injection molded to prepare a specimen, and the physical properties were measured by the following method, and the results are shown in Table 1 below.

* Impact Strength (kg-cm / cm)-Measured on a 1/8 ”thick specimen in accordance with ASTM D256.

* Heat resistance (℃)-The heat deflection temperature was measured on a 1/4 ”thick specimen in accordance with ASTM D648.

* Flame retardancy-Measured on 1/8 ”thick specimens in accordance with UL94 VB flame retardant specification.

[Table 1]

division Example Comparative example One 2 3 One 2 3 Resin composition
(Parts by weight) Rubber modified styrene-containing graft copolymer 20 20 20 20 20 20 Styrene-containing copolymer 65 65 65 65 65 65 Cresol Novolak
Epoxy 15 15 15 15 15 Phenolic resin - - - - - 15 Phosphite compounds 5 12 15 - - 15 Phosphate Ester Compound - - - - 15 - Impact strength (㎏? ㎝ / ㎝) 19 30 30 13 3 31 Heat deformation temperature (캜) 71 75 75 68 55 76 White index 24.4 24.5 24.6 24.2 24.3 -32.3 Yellow index 19.0 18.9 18.9 19.1 19.0 42.9 Weatherability (ΔE) 8.0 7.7 7.5 8.3 9.2 34.2 Flame retardancy NR (S / O) V-1 V-1 NR (B / O) V-1 V-1 * NR: No Rating, S / O: Spec out, B / O: Burn Out

Through Table 1, the thermoplastic flame-retardant resin composition of Examples 1, 2 and 3 containing a suitable range of the phosphite compound as a flame retardant in the base resin according to the present invention has an impact strength, heat resistance and flame retardancy It was confirmed that it was excellent.

On the other hand, in Comparative Example 1, which does not include a flame retardant, the flame retardancy, impact strength, and heat distortion temperature were significantly lowered. In addition, Comparative Example 2 containing a phosphate ester-based compound as a flame retardant, the flame retardancy was the same as in Example, but showed a sharp decrease in the heat deformation temperature and impact strength.

Comparative Example 3, in which a phenol resin was used as the char forming agent, showed a very low white index and a very high yellow index as well as a markedly poor weather resistance result compared to other examples using cresol novolac epoxy as a char forming agent.

As a result, by using a phosphite compound as a flame retardant and a cresol novolac epoxy as a char forming agent, it can be seen that a resin having not only excellent flame retardancy, heat resistance and impact resistance, but also easy to realize white color and excellent weather resistance can be produced. have.

Although described in detail above with reference to the specific embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.

Claims (14)

Basic resin consisting of 9 to 80% by weight of rubber-modified styrene compound-containing graft copolymer, 19 to 90% by weight of styrene-based compound containing copolymer, and 1 to 30% by weight of epoxy resin having the structure A thermoplastic flame-retardant resin composition comprising 1 to 30 parts by weight of a phosphite compound having a structure of Formula 2 with respect to 100 parts by weight of the base resin. [Formula 1]

In Chemical Formula 1, n is from 1 to 10000, [Formula 2]

In Chemical Formula 2, R ₁ to R ₃ are an alkyl group or an aryl group. The method of claim 1, The rubber-modified styrenic compound-containing graft copolymer is a thermoplastic flame-retardant resin composition characterized in that the graft copolymer 30 to 65% by weight of the styrene compound and 10 to 30% by weight of the acrylic compound in 10 to 60% by weight of the rubber component. 3. The method of claim 2, The rubber component is a thermoplastic flame retardant resin composition, characterized in that at least one selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene and butadiene-isoprene copolymer. 3. The method of claim 2, The styrene-based compound is a thermoplastic flame-retardant resin composition, characterized in that at least one selected from the group consisting of styrene, alphamethyl styrene and nuclear substituted styrene. 3. The method of claim 2, The acrylic compound is at least one member selected from the group consisting of acrylonitrile, methyl methacrylate and butyl acrylate, thermoplastic flame retardant resin composition. The method of claim 1, The rubber-modified styrene compound-containing graft copolymer may be acrylonitrile-butadiene-styrene graft copolymer (ABS resin), acrylonitrile-ethylenepropylene rubber-styrene graft copolymer (AES resin), or acryl A nitrile-acrylic rubber-styrene graft copolymer (AAS resin), characterized in that the thermoplastic flame-retardant resin composition. The method of claim 1, The styrene-based compound-containing copolymer is a thermoplastic flame-retardant resin composition, characterized in that 50 to 80% by weight of the styrene-based compound and 20 to 50% by weight of the acrylic compound. The method of claim 7, wherein The styrene-based compound is a thermoplastic flame-retardant resin composition, characterized in that at least one selected from the group consisting of styrene, alphamethyl styrene and nuclear substituted styrene. The method of claim 7, wherein The acrylic compound is at least one member selected from the group consisting of acrylonitrile, methyl methacrylate and butyl acrylate thermoplastic flame retardant resin composition. The method of claim 1, The phosphite compound is selected from the group consisting of trialkyl phosphite, alkyldiaryl phosphite, dialkylaryl phosphite, and triaryl phosphite. Thermoplastic flame retardant resin composition, characterized in that at least one selected. The method of claim 10, The trialkyl phosphite (trialkyl phosphite) thermoplastic flame retardant resin composition, characterized in that it has an alkyl group having 1 to 10 carbon atoms. The method of claim 10, The alkyldiaryl phosphite is nonyldiphenyl phosphite or isodecyldiphenyl phosphite, and the dialkylaryl phosphite is dinonylphenyl phosphite. Thermoplastic flame retardant composition, characterized in that dinonylphenyl phosphite) or diisodecylphenyl phosphite (diisodecylphenyl phosphite). The method of claim 1, The phosphite compound is a thermoplastic flame retardant resin composition, characterized in that triaryl phosphite substituted with an alkyl group (triaryl phosphite). The method of claim 1, The thermoplastic flame retardant resin composition further comprises at least one additive selected from lubricants, heat stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers.