KR20060042044A - Nanocomposite thermoplast non-halogen resin composition with flame resistance - Google Patents

Abstract

The present invention relates to a nanocomposite flame retardant thermoplastic resin composition comprising a compatibilizer, a melamine-based flame retardant and an organic layered silicate in a base resin mixture consisting of a rubber modified styrene containing graft copolymer, a thermoplastic polyamide resin and a styrene containing copolymer. The nanocomposite flame retardant thermoplastic resin composition of the present invention may exhibit excellent flame retardancy even without using a halogen-based flame retardant.

Melamine Flame Retardant, Organic Layered Silicate

Description

Nanocomposite thermoplast non-halogen resin composition with flame resistance}

The present invention relates to a nanocomposite flame retardant thermoplastic resin composition comprising a compatibilizer, a melamine-based flame retardant and an organic layered silicate in a base resin mixture consisting of a rubber modified styrene containing graft copolymer, a thermoplastic polyamide resin and a styrene containing copolymer. .

Rubber modified styrene-containing graft copolymers have excellent processability and physical properties, and are excellent in appearance and impact strength, so they are widely used in electrical and electronic products and office equipment. In addition, polyamide resins have excellent mechanical, thermal, and chemical properties and are used for mechanical parts and electrical and electronic materials. Therefore, when the two materials are blended, synergistic effects can be obtained through the moisture resistance and dimensional stability of the styrene-containing graft copolymer and the excellent mechanical, thermal and chemical properties of the polyamide resin.

On the other hand, electrical and electronic products and office equipment generates a lot of heat in use, so there is a risk of fire, the resin used should be flame retardant.

The flame retardant method of rubber modified styrene-containing graft copolymer is known to be the most effective to use a halogen-based compound as a flame retardant. Tetrabromobisphenol A and brominated epoxy is the most commonly used halogen flame retardant and antimony It is also well known that compounds play a role in increasing flame retardancy.

However, halogen-based compounds are known to generate gases that corrode molds during processing and 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, and they are regulated for use around Europe. Antimony compounds are also classified as toxic substances.

Accordingly, much attention has been focused on the study of the composition of a flame retardant resin that does not use halogen compounds and antimony. Phosphorus-based flame retardants, melamine-based flame retardants and the like are widely used in flame retardant resin compositions that do not use halogen compounds and antimony.

On the other hand, the clay dispersion nanocomposite manufacturing technology is to make the limit of low mechanical properties of the general-purpose polymer to the level of engineering plastics by peeling the silicate layered clay minerals into the nano-scale plate-shaped base unit and dispersed in the polymer resin.

Accordingly, the present invention provides a nanocomposite flame retardant thermoplastic resin composition having excellent flame retardancy by using a melamine-based flame retardant and an organic layered silicate in a resin mixture blended with a rubber modified styrene-containing graft copolymer and a thermoplastic polyamide resin. have.

In order to achieve the above object, the present invention

a) with respect to 100 parts by weight of a base resin mixture composed of 2 to 79% by weight of rubber-modified styrene-containing graft copolymer, 18 to 95% by weight of thermoplastic polyamide resin, and 3 to 80% by weight of styrene-containing copolymer,

b) 0.1 to 15 parts by weight of a compatibilizer,

c) 5 to 30 parts by weight of melamine flame retardant and

d) A nanocomposite flame retardant thermoplastic resin composition comprising 0.01 to 10 parts by weight of an organic layered silicate is provided.

MEANS TO SOLVE THE PROBLEM The present inventors added the melamine type flame retardant and the organic layered silicate, and improved the flame retardance and the physical property, while maintaining the advantage through the blending of a rubber modified styrene containing graft copolymer and a thermoplastic polyamide resin, and the composite composite flame retardant thermoplastic resin composition The present invention has been completed by the development.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

(1) Rubber Modified Styrene-Containing Graft Copolymer

The rubber modified styrene-containing graft copolymer used in the present invention is 30 to 65% by weight of one or more styrene resins selected from the group consisting of styrene, alphamethyl styrene and nuclear substituted styrene and acrylonitrile, methyl methacrylate and butylacryl. Graft to 10 to 60% by weight of at least one rubber selected from the group consisting of butadiene, styrene-butadiene copolymer, isoprene and butadiene-isoprene copolymer Resin.

The graft copolymer may be prepared by a conventional polymerization method, but is preferably synthesized by bulk polymerization or emulsion polymerization. In particular, acrylonitrile / butadiene / styrene (ABS) resins in which acrylonitrile and styrene are grafted to butadiene rubber are widely used.

The rubber modified styrene-containing graft copolymer is preferably used in the range of 2-79% by weight in the total base resin mixture. If the amount of the rubber-modified styrene-containing graft copolymer is less than 2% by weight, the notch impact strength is lowered. If the rubber-modified styrene-containing graft copolymer is used, the rigidity and toughness are lowered.

 (2) thermoplastic polyamide resin

Polyamide resin used in the present invention is nylon 6, nylon 46, nylon 66, nylon 69, nylon 610, nylon 6/66, nylon 612, nylon 611, nylon 11, nylon 12, nylon 61, nylon 6T, / 6I, Nylon 66 / 6T, polybis (4-aminocyclohexyl) methanedodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methanedodecamide (nylon dimethyl PACM12), polymethylene Adipamide (MXD6), polyundecamethylene terephthalamide (nylon 11T), and polyundeca methylenehexahydroterephthalamide (nylon 11T (H)), where I stands for isophthalic acid and T stands for terephthalic acid. . And mixtures or copolymers of two or more of the above compounds may be used.

Of these polyamides, it is preferable to use nylon 6, nylon 46, nylon 66, nylon 11, nylon 12, nylon 610 and mixtures or copolymers thereof. Most preferably, nylon 6 is used.

For the mechanical, thermal and chemical properties imparted by the polyamide, the relative viscosity of the polyamide is preferably 1.5 to 5.0. If the relative viscosity is lower than 1.5, it is difficult to show the desired physical properties. If the relative viscosity is higher than 5.0, manufacturing cost increases and processing difficulties occur. On the other hand, the polyamide can know the simple measurement value of a polymerization degree from a relative viscosity measurement.

Polyamide is used in the range of 18 to 95% by weight of the total base resin. If the amount of the polyamide is less than 18% by weight, deterioration of mechanical properties is caused, and if it exceeds 95% by weight, the notch impact strength is weakened.

In addition, the polyamide may be copolymerized with other copolymerizable components, if necessary.

The polyamide used in the present invention may be produced by melt polymerization or solid state polymerization.

The polyamide / rubber modified styrene-containing graft copolymer blend, as mentioned above, has excellent mechanical, thermal and chemical properties of the polyamide material and excellent impact, dimensional stability, paint adhesion and appearance properties of the rubber modified styrene-containing copolymer. It expresses the synergy effect of crystalline polymer and amorphous polymer by expressing (Good Appearance) as cross-linked properties.

(3) styrene-containing copolymer

The styrene-containing copolymer used in the present invention is 50 to 80% by weight of one or more styrene compounds selected from styrene, alphamethyl styrene and nuclear substituted styrene, and one or more acrylics selected from acrylonitrile, methyl methacrylate and butyl acrylate. It consists of 20-50 wt% of the compound. The graft copolymer resin may be prepared by a conventional polymerization method, but is preferably prepared by bulk polymerization or emulsion polymerization.

The styrene-containing copolymer is used in the range of 3 to 80% by weight in the total base resin. If the amount of the styrene-containing copolymer is less than 3% by weight, the dimensional stability deteriorates. If the amount of the styrene-containing copolymer exceeds 80% by weight, the impact strength is lowered.

The main components in the composition of the present invention are polyamide and rubber modified styrene-containing graft copolymers (usually ABS, ASA, AES, HIPS and the like but mainly ABS). ABS is typically an interpolymer of a rubber modified styrene-containing graft copolymer and a styrene-containing copolymer. The former is responsible for the impact properties of the resin composition and the latter is responsible for the stiffness and heat resistance. Properties can be controlled by the ratio.

(4) compatibilizer

Compounds that can be used as compatibilizers of the present invention include styrene-maleic anhydride copolymers, acrylonitrile-butadiene-styrene-styrene-maleic anhydride grafting copolymers (ABS-g-MA) or methyl methacrylate (MMA), acrylics Ronitrile-styrene-maleic anhydride grafting copolymer (AS-g-MA) and the like, and preferably, styrene-maleic anhydride copolymer and acrylonitrile-styrene-maleic anhydride grafting copolymer.

The styrene-maleic anhydride copolymer may be prepared by treating styrene with maleic anhydride. Styrene-maleic anhydride copolymer (SMA) is compatible with styrene-containing copolymers or rubber-modified styrene-containing copolymers, and reacts with polyamides as shown in Scheme 1 to express compatibility.

[Scheme 1]

It is preferable to use a compatibilizer in 0.1-15 weight part with respect to 100 weight part of total base resins. If the compatibilizer is not used, there is no compatibility between the polyamide which is a crystalline resin and the rubber modified styrene-containing graft copolymer which is an amorphous resin, and thus it is difficult to express the excellent characteristics of the resins. Many crosslinking resistance arises and workability becomes very bad.

(5) melamine flame retardant

Melamine-based flame retardants used in the present invention include melamine or melamine derivatives, for example melamine, cyanuric acid melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and the like.

Melamine-based flame retardant is preferably used in 5 to 30 parts by weight based on 100 parts by weight of the total base resin. If the melamine-based flame retardant is used in less than 5 parts by weight, flame retardancy is lowered, and when used in excess of 30 parts by weight, the impact strength is lowered.

(6) organic layered silicate

The organic layered silicate used in the present invention is an organic material of a layered silicate selected from the group consisting of montmorillonite, hectorite, vermiculite and saponite. Alkyl ammonium, alcohols, ketones, and the like may be used as the organic agent to facilitate peeling and dispersion of the organic layered silicate to a nano size in the polymer. Preferably, polyvinyl alcohol can be used among alcohols.

In addition, the nanocomposite flame retardant thermoplastic resin composition of the present invention may further include one or more selected from the group consisting of lubricants, thermal stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers. The lubricants, heat stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments or inorganic fillers may be any additives generally used in the art.

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

The styrene-based thermoplastic resin composition used in the following Examples and Comparative Examples includes (1) rubber modified styrene-containing graft copolymers, (2) thermoplastic polyamide resins, (3) styrene-containing copolymers (4) compatibilizers, ( 5) Melamine-based flame retardant, (6) organic layered silicate, the production method and specifications thereof are as follows.

(1) Rubber modified styrene-containing graft copolymer

Rubber modified styrene-containing graft copolymer used in the present invention was used by LG Chemical. This resin is acrylonitrile / butadiene / styrene resin grafted acrylonitrile and styrene on butadiene rubber and consists of 14% by weight of acrylonitrile, 36% by weight of styrene and 50% by weight of butadiene rubber. It is synthesized by emulsion polymerization method as known in the art.

(2) thermoplastic polyamide resin

In the thermoplastic polyamide resin used in the present invention, nylon 6 was prepared by ring-opening polymerization of ε-caprolactam in the presence of water.

(3) styrene-containing copolymer

As the styrene-containing copolymer, LG Chem SAN ^® Co., Ltd. product was used.

(4) compatibilizer

The compatibilizer used in the present invention used SMA ^® EF-30 from ATOFINA, a styrene-maleic anhydride copolymer.

(5) melamine flame retardant

Melamine-based flame retardant used in the present invention used Melapur ^® MC25 (melamine cyanurate) from DSM.

(6) organic layered silicate

10 g of montmorillonite was dispersed in 1000 ml of tertiary distilled water using a sonicator, and 10 g of polyvinyl alcohol having a degree of polymerization of 600 was completely dissolved in 1000 ml of distilled water. Then, 1000 ml of polyvinyl alcohol solution was added to 1010 ml of montmorillonite dispersion aqueous solution, and the mixture was sufficiently stirred for 3 hours. It was dried in a vacuum dryer. The dried reactant was ground to prepare a powder.

<Example 1>

1 part by weight of SMA ^® EF-30 as a compatibilizer, based on 100 parts by weight of the total resin consisting of 14% by weight of rubber modified styrene-containing graft copolymer, 65% by weight of thermoplastic polyamide resin and 21% by weight of styrene-containing copolymer. the Melapur ^® MC25 (melamine-cyanuric acid), 5 parts by weight of a flame-retardant thermoplastic resin composition using an organic layered silicate (PVA-modified-MMT) 1 parts by weight was prepared.

<Example 2>

Except that the increase of Melapur MC25 ^® 10 parts by weight of a flame retarder was prepared in the same manner as in Example 1.

<Example 3>

Except that 10 parts by weight of SMA ^® EF-30 as a compatibilizer, 20 parts by weight of Melapur ^® MC25 (melamine cyanurate melamine) as a flame retardant, and 5 parts by weight of organic layered silicate was prepared in the same manner as in Example 1.

<Example 4>

30 parts by weight of Melapur MC25 ^® (cyanuric acid melamine) as the flame retardant, and have been prepared in the same manner as in Example 1 except that an organic layered silicate, 5 parts by weight.

Comparative Example 1

Flame retardant was produced by the same procedures as those in Example 1 except for using 3 parts by weight of Melapur MC25 ^®.

Comparative Example 2

The Melapur ^® MC25 as the flame retardant and was prepared in the same manner as in Example 1 except for using 35 parts by weight.

Comparative Example 3

It was prepared in the same manner as in Example 2 except that no compatibilizer was used.

<Comparative Example 4>

It was prepared in the same manner as in Example 2 except for using a total resin composed of 40% by weight of rubber-modified styrene-containing graft copolymer and 60% by weight of styrene-containing copolymer.

Comparative Example 5

It was prepared in the same manner as in Example 2 except that no organic layered silicate was used.

Experimental Example 1

Table 1 shows the results of measuring the tensile strength, impact strength and flame retardancy of the compositions of Examples 1 to 4 and Comparative Examples 1 to 5 and the specimens prepared accordingly. Tensile strength was measured according to ASTM D-638, impact strength was measured according to ASTM D-256 conditions, and flame retardancy was measured according to the UL94 VB flame retardant standard.

 Example  Comparative example  One  2  3  4  One  2  3  4  5  Acrylonitrile / butadiene / styrene  14  14  14  14  14  14  14  40  14 Polyamide  65  65  65  65  65  65  65  -  65  Styrene-containing copolymer  21  21  21  21  21  21  21  60  21 SMA ^® EF-30  One  One  10  One  One  One  -  One  One Melapur ^® MC 25  5  10  20  30  3  35  10  10  10  PVA-modified-MMT  One  One  5  5  One  One  One  One  - Tensile Strength (kg / cm ² ) 753 742 729 696 761 669 478 521  720  Impact Strength (1/4 ") 27 24 15 11 21 4 3 26  23  Flame Retardant (1/8 ") V-1 V-0 V-0 V-0 X V-0 V-0 X V-1

If the blending carried out for the polyamide resin, SMA ^® EF-30 in styrene-based copolymer as in Examples 1 to 4 and the addition of the melamine-based flame retardant exhibited a superior flame retarding FIG. However, when using less than 5 parts by weight of the melamine flame retardant as shown in Comparative Example 1, when using more than 30 parts by weight of melamine based flame retardant as shown in Comparative Example 2 is excellent in flame retardancy but impact strength is lowered Could know. In addition, when the compatibilizer is not used as in Comparative Example 3, the flame retardancy is excellent, but the mechanical strength such as tensile strength and impact strength was significantly reduced. When the melamine-based flame retardant was used in the resin using the styrene-based copolymer alone as in Comparative Example 4, the flame retardant did not show sufficient flame resistance. However, in the case of Example 2 blended with the polyamide resin, excellent flame retardancy was obtained. Comparing the flame retardancy of Example 2 using the organic layered silicate and Comparative Example 5 not used, it was confirmed that the flame retardancy was better when the organic layered silicate was used, and that the tensile strength was also higher in Example 2.

As described above, the present invention uses a halogen-based flame retardant by adding a compatibilizer, a melamine-based flame retardant and an organic layered silicate to a base resin mixture composed of a rubber modified styrene-containing graft copolymer, a thermoplastic polyamide resin and a styrene-containing copolymer. The nanocomposite flame retardant thermoplastic resin composition excellent in flame retardancy can be prepared without.

Claims (8)

a) with respect to 100 parts by weight of a base resin mixture composed of 2 to 79% by weight of rubber-modified styrene-containing graft copolymer, 18 to 95% by weight of thermoplastic polyamide resin, and 3 to 80% by weight of styrene-containing copolymer, b) 0.1 to 15 parts by weight of a compatibilizer, c) 5 to 30 parts by weight of melamine flame retardant and d) A nanocomposite flame retardant thermoplastic resin composition comprising 0.01 to 10 parts by weight of an organic layered silicate. The styrene and alphamethyl styrene according to claim 1, wherein the rubber-modified styrene-containing graft copolymer is 10 to 60 wt% of at least one rubber selected from the group consisting of butadiene, styrene-butadiene copolymer, isoprene and butadiene-isoprene copolymer. 30 to 65% by weight of one or more styrene resins selected from the group consisting of nuclear substituted styrenes; And 10 to 30% by weight of an acrylic resin selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate. The nanocomposite flame retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic polyamide resin is made of a polymer having a relative viscosity of 1.5 to 5.0. The group according to claim 1, wherein the styrene-containing copolymer is composed of 50 to 80% by weight of at least one compound selected from the group consisting of styrene, alphamethyl styrene and nuclear substituted styrene and acrylonitrile, methyl methacrylate and butyl acrylate. Nanocomposite flame-retardant thermoplastic resin composition comprising 20 to 50% by weight of at least one compound selected from. The method of claim 1 wherein the compatibilizer is styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene-maleic anhydride grafting copolymer (ABS-g-MA), methyl methacrylate (MMA) and acrylonitrile- Nanocomposite flame retardant thermoplastic resin composition, characterized in that at least one selected from the group consisting of styrene-maleic anhydride grafting copolymer (AS-g-MA). The nanocomposite flame retardant thermoplastic resin composition of claim 1, wherein the melamine-based flame retardant is selected from the group consisting of melamine, cyanuric acid melamine, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate. The method of claim 1, wherein the organic layer silicate is selected from the group consisting of montmoryl ronite, hectorite, vermiculite and saponite organicized with an organic agent selected from the group consisting of alkylammonium, alcohols having a degree of polymerization of 5 to 1000 and ketones. Nanocomposite flame retardant thermoplastic resin composition, characterized in that the layered silicate. The nanocomposite flame retardant thermoplastic resin composition of claim 1, further comprising at least one selected from the group consisting of lubricants, thermal stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments, and inorganic fillers. Composite thermoplastic resin composition.