KR101118197B1 - Flameproof Thermoplastic Resin Composition - Google Patents

Abstract

The flame retardant thermoplastic resin composition according to the present invention is an aromatic vinyl resin, a rubber modified aromatic vinyl resin, a polyphenylene ether resin, a polycarbonate resin, a polyester resin, a methacrylate resin, a polyarylene sulfide resin , 100 parts by weight of (A) thermoplastic resin selected from the group consisting of polyamide-based resins, polyvinyl chloride-based resins, polyolipine-based resins and mixtures of two or more thereof, and (B) selenium-based flame retardants represented by the following general formula (2): It is characterized by comprising 0.1 to 40 parts by weight:

[Formula 2]

Wherein R ₁ and R ₂ are each independently a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₂₀ aryl group or a C ₆ -C ₂₀ aryl group substituted with a C ₁ -C ₁₀ alkyl group.

Phosphorus flame retardant, flame retardant, thermoplastic resin composition, selenium compound, non-halogen flame retardant, aromatic vinyl resin

Description

Flameproof Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition incorporating a non-halogen-based and non-phosphorus-based flame retardant. More specifically, the present invention relates to a flame-retardant thermoplastic resin composition which is environmentally friendly and excellent in flame retardancy compared to conventional phosphorus-based flame retardants by applying a new selenium flame retardant instead of an existing phosphorus-based flame retardant based on an aromatic vinyl resin or a polycarbonate resin.

Background of the Invention

Recently, the use of plastic polymers or synthetic resins has been diversified, such as vehicles, building materials, aircraft, railways, and home appliances, and as the development of various functional additives is rapidly progressing, its application range is explosively increasing. However, the plastic itself has the property of easy combustion and is not resistant to fire. Therefore, the plastic can be easily burned by the external ignition source, and may serve to spread the fire more. In light of this, countries such as the US, Japan, and Europe regulate the use of polymer resins that meet the flame retardant standards to ensure the safety of fires in electronic products.

Flame retardant methods for polymers include the synthesis of thermally stable resins through design or molecular structure design, chemical modification of existing polymers (reactive), physical additions through blending or compounding of flame retardants (additives), coating or painting of flame retardants Method and the like. The most widely known flame retardant method is to add a flame retardant to the polymer resin. Additive flame retardants are classified into halogen-based, phosphorus-based, nitrogen-based, silicon-based and inorganic flame-retardants depending on the constituents.

Halogen-based flame retardant plays a role of suppressing the chain reaction of the combustion process through the reaction with radicals generated in the gas phase during the combustion process of the polymer in the resin. As the halogen-based compound, polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compound, and chlorinated polyethylene are mainly used as antimony trioxide and antimony pentoxide. The application of halogen and antimony compound together to impart flame retardancy has the advantage of easy flame retardancy and little deterioration of physical properties.However, experiments have shown that hydrogen halide gas generated during processing may have a fatal effect on the human body. Is being reported.

On the other hand, bromine-based flame retardants are most widely used because of their unique properties, price, and excellent flame retardancy, especially in the electric and electronic fields, but they also cause environmental problems because they are likely to generate very toxic gases such as dioxins and furans. As the RoHS (Restriction of Use of Hazardous Substances in Electrical and Electronic Products) came into effect in July 2006, some of the general-purpose bromine-based flame retardants, also known as deca, have been discontinued, and their use has decreased dramatically.

A technique for imparting flame retardancy without using a halogen flame retardant is currently the most common is to use a phosphorus flame retardant. Such phosphorus-based flame retardants exhibit excellent flame retardant effects in the reaction of solid phase, and are particularly effective for plastics containing a large amount of oxygen. U.S. Patent 4,692,488 discloses thermoplastic resin compositions consisting of non-halogen aromatic polycarbonate resins, non-halogen styrene-acrylonitrile copolymers, non-halogen phosphorus compounds, tetrafluoroethylene polymers and small amounts of ABS copolymers. U.S. Patent 5,061,745 discloses a flame retardant resin composition composed of an aromatic polycarbonate resin, an ABS graft copolymer, a copolymer and a monomeric phosphoric acid ester.

Representatives used as flame retardants among the phosphorus compounds are commercially available aromatic phosphate esters, but since the phosphorus content is lower than 10%, it is still necessary to use a large amount to achieve flame retardancy. In addition, there is a problem in that the resin composition using the flame retardant is moved to the surface of the molding during molding, so that a surface crack, that is, a "juice" phenomenon occurs, and the heat resistance of the resin composition is sharply lowered. In addition, its use range is limited due to its compatibility, and there are problems such as securing a stable supply line.

Other phosphorus compound flame retardants include phosphazene compounds. EP 728,811 discloses a flame retardant resin composition composed of an aromatic polycarbonate resin, a graft copolymer, a vinyl copolymer and a phosphazene compound. This patent shows that phosphazene compound can be used as a flame retardant so that no dropping occurs during combustion without a separate antidropping agent, and excellent heat resistance and impact strength can be obtained. However, when the phosphazene compound is used as a flame retardant, there is a problem that many flame retardants must be used in order to exhibit excellent flame retardant grades.

In order to solve the problems of the conventional halogen-based flame retardant and phosphorus-based flame retardant, the present inventors applied selenium compounds as novel flame retardants based on thermoplastic resins such as aromatic vinyl resins, polyphenylene ether resins, and polycarbonate resins. It is to develop a flame retardant thermoplastic resin composition excellent in stability and fire stability and excellent flame retardancy compared to the existing products.

An object of the present invention is to provide a flame retardant thermoplastic resin composition that is stable against fire.

It is another object of the present invention to provide an environmentally friendly flame retardant thermoplastic resin composition by using an environmentally friendly compound as a flame retardant without using a halogen flame retardant or phosphorus flame retardant with limited compatibility, which causes environmental pollution during resin processing or combustion. It is to.

Another object of the present invention to provide a plastic molded article excellent in flame retardancy compared to the existing product using the composition.

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

Summary of the Invention

The flame retardant thermoplastic resin composition according to the present invention is characterized in that it comprises 100 parts by weight of (A) thermoplastic resin and 0.1 to 40 parts by weight of (B) selenium-based flame retardant. The thermoplastic resin (A) is aromatic vinyl resin, rubber modified aromatic vinyl resin, polyphenylene ether resin, polycarbonate resin, polyester resin, methacrylate resin, polyarylene sulfide resin, poly It is characterized in that it is selected from the group consisting of an amide resin, a polyvinyl chloride resin, a polyolipine resin and a mixture of two or more thereof.

In one embodiment, the thermoplastic resin (A) may be composed of 50 to 99% by weight of aromatic vinyl resin and 1 to 50% by weight of polyphenylene ether resin. In another embodiment, the thermoplastic resin (A) may be composed of 0 to 70 wt% of the rubber-modified aromatic vinyl resin and 30 to 100 wt% of the polycarbonate resin.

The resin composition may further include an additive selected from the group consisting of flame retardant aids, plasticizers, thermal stabilizers, anti-drip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives and mixtures thereof.

The present invention provides a molded article having a flame retardancy of 0/8 "thick according to UL94 VB manufactured using the flame retardant thermoplastic resin composition.

Hereinafter, the content of the present invention will be described in detail below.

Detailed Description of the Invention

The present invention provides a flame retardant thermoplastic resin composition comprising 100 parts by weight of (A) thermoplastic resin and 0.1 to 40 parts by weight of (B) selenium-based flame retardant. Hereinafter, each said component is demonstrated in detail.

(A) thermoplastic resin

As the thermoplastic resin that can be used in the present invention, all resins having thermoplastics can be used, and there is no particular limitation. For example, aromatic vinyl resin, rubber modified aromatic vinyl resin, polyphenylene ether resin, polycarbonate resin, polyester resin, methacrylate resin, polyarylene sulfide resin, polyamide resin, polychlorinated Vinyl-based resins, polyolefin resins, etc. may be used, but are not necessarily limited thereto. The thermoplastic resin may be applied alone or in combination of two or more.

In one embodiment, the thermoplastic resin may include a polymer having a weight average molecular weight (Mw) of 10,000 or more.

(A1) aromatic vinyl resin

In the present invention, the aromatic vinyl resin may include a homopolymer obtained by homopolymerizing an aromatic vinyl monomer or a rubber-modified aromatic vinyl resin obtained by polymerizing an aromatic vinyl monomer with a rubber polymer, and mixing a rubber polymer with an aromatic vinyl monomer. And a mixture of unsaturated nitrile monomers.

The rubbery polymer may include butadiene rubber, isoprene rubber, copolymer of butadiene and styrene, acrylic rubber such as alkyl acrylate, ethylene-propylene-diene terpolymer rubber (EPDM), ethylene-propylene rubber, silicone rubber, and the like. It is not necessarily limited thereto. The rubbery polymer may be used alone or in mixture of two or more thereof. The rubbery polymer may be used in 3 to 30% by weight, preferably 5 to 15% by weight of the aromatic vinyl resin. In addition, in order to exhibit optimal physical properties in the blend of the aromatic vinyl resin and the polyphenylene ether resin, the rubber polymer preferably has a particle size of 0.1 to 4.0 µm.

The aromatic vinyl monomer may be used in 70 to 97% by weight, preferably 85 to 95% by weight. The aromatic vinyl monomers include styrene, α-methyl styrene, vinyl toluene, and the like, which may be used alone or in combination of two or more thereof.

In addition, other monomers copolymerizable with the aromatic vinyl monomer may be applied together. The copolymerizable monomer may be acrylonitrile, methacrylonitrile, alkyl (meth) acrylate, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, epoxy group-containing monomers, and the like. It can be used by mixing the above. The amount to be added of the copolymerizable monomer is 40% by weight or less, preferably 0.01 to 40% by weight, and more preferably 0.1 to 25% by weight based on the whole aromatic vinyl resin.

In specific embodiments, examples of the aromatic vinyl resin may be GPPS, sPS, HIPS, ABS, ASA, SAN, MSAN, MABS, and the like, and these may be applied alone or in combination of two or more thereof.

In the polymerization of the resin composition according to the present invention, it can be carried out by thermal polymerization without the presence of an initiator and can also be carried out in the presence of an initiator. Polymerization initiators that can be used include one or more selected from peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumenehydro peroxide, and azo initiators such as azobis isobutyronitrile. Can be. The aromatic vinyl-based resin may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, a bulk polymerization method of these polymerization methods may be preferably used.

(A2) polyphenylene ether resin

In the present invention, polyphenylene ether resin may be added to further improve flame retardancy and heat resistance. Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-di Propyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene ) Copolymer of poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,5) A copolymer of -triethyl-1,4-phenylene) ether. Although the polymerization degree of the said polyphenylene ether is not specifically limited, It is preferable that the intrinsic viscosity measured in 25 degreeC chloroform solvent is 0.2-0.8 in consideration of the thermal stability and workability of a resin composition.

(A3) polycarbonate resin

The polycarbonate-based resin (A) used in the production of the resin composition of the present invention is well known and can be easily purchased commercially. In one embodiment, the polycarbonate-based resin (A) may be prepared by reacting hydroquinone, resorcinol, or diphenols represented by the following Formula 1 with phosgene, halogen formate, or carbonic acid diester.

[Formula 1]

(Wherein A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO _2- )

Specific examples of the formula (1) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2 -Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3, 5-dichloro-4-hydroxyphenyl) -propane etc. are mentioned. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Hydroxyphenyl) -cyclohexane and the like are preferred, of which 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A, is most preferred industrially.

Suitable polycarbonates used in the preparation of the resin composition of the present invention include those having a weight average molecular weight of 10,000 to 200,000, preferably 15,000 to 80,000.

As the polycarbonate used in the preparation of the resin composition of the present invention, a branched chain may be used, preferably 0.05 to 2 mol% of a tri- or more polyfunctional compound based on the total amount of diphenols used for polymerization, For example, it may be prepared by adding a compound having a trivalent or more phenol group.

Examples of the polycarbonate used in the production of the resin composition of the present invention include homo polycarbonates and copolycarbonates, and may also be used in the form of a blend of copolycarbonates and homo polycarbonates. In addition, the polycarbonate used in the production of the resin composition of the present invention may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid.

In addition, the thermoplastic resin may also be used a terephthalic acid ester resin such as polyethylene terephthalate or polybutylene terephthalate.

As the thermoplastic resin of the present invention, methacrylate resin may be used. The methacrylate-based resin is a copolymer of 50 to 100% by weight of methyl methacrylate (MMA) and 0 to 50% by weight of monofunctional unsaturated monomer. The monofunctional unsaturated monomer is not particularly limited as a copolymerizable monomer, and meta, such as ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate, phenyl methacrylate and glycidyl methacrylate. Acrylates such as acrylate methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Acid anhydrides such as unsaturated carboxylic acids such as acrylic acid and methacrylic acid, maleic anhydride and the like; And monofunctional vinyl group-containing monomers such as styrene, acrylonitrile, and methacrylonitrile. These can be applied individually or in mixture of 2 or more types.

In another embodiment, the thermoplastic resin may be a polyolefin resin. Polyethylene, polypropylene, and the like may be used as the polyolefin resin, and a modified polyolefin modified with a glycidyl group or a (meth) acrylate group may be used. The polyethylene may be in any form such as HDPE, LDPE, LLDPE, and any structure such as atactic, syndiotactic, isotactic, or the like may be used. It may also be used in the form of copolymerization of polyolefins with monomers having other ethylenically unsaturated groups.

The thermoplastic resin of the present invention is not limited to the resins exemplified above, and may be applied in the form of alloy alone or in combination of two or more thereof.

In one embodiment, the thermoplastic resin may include 50 to 99 parts by weight of an aromatic vinyl resin and 1 to 50 parts by weight of a polyphenylene ether resin. In another embodiment, the thermoplastic resin may include 0 to 70 parts by weight of a rubber-modified aromatic vinyl resin and 30 to 100 parts by weight of a polycarbonate resin. In another embodiment, the thermoplastic resin may be composed of 50 to 70% by weight of a polycarbonate resin and 30 to 50 parts by weight of a rubber-modified aromatic vinyl resin.

(B) selenium flame retardant

Selenium-based flame retardants may be used as the flame retardant of the present invention. The selenium-based flame retardant is a selenium-based compound represented by the following Chemical Formula 2 and may express excellent flame retardancy with respect to the thermoplastic resin composition. In Formula 2, wherein R ₁ and R ₂ are each independently a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₂₀ aryl group or a C ₆ -C ₂₀ aryl group substituted with a C ₁ -C ₁₀ alkyl group, It is preferably a phenol group.

[Formula 2]

Wherein R ₁ and R ₂ are each independently a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₂₀ aryl group or a C ₆ -C ₂₀ aryl group substituted with a C ₁ -C ₁₀ alkyl group

In the present invention, the selenium-based flame retardant is used 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 25 parts by weight based on 100 parts by weight of the thermoplastic resin. When the selenium-based flame retardant content is applied at 0.1 or less, flame retardancy of V-0 or V-1 may not be obtained, and when it exceeds 40 parts by weight, impact strength may be lowered.

Selenium-based compound represented by the following formula (2) is easy to commercial purchase, it can be easily prepared by those skilled in the art to which the present invention belongs.

In another embodiment, a flame retardant aid may be applied in conjunction with the flame retardant. In an embodiment, antimony oxide may be applied as the selenium flame retardant and the flame retardant aid. The antimony oxide may also be applied to antimony trioxide, antimony pentoxide or a mixture thereof. In embodiments, the antimony oxide may be used that contains an antimony content of 75 to 90% by weight. In the case of the antimony trioxide, 50% particle size of 0.01 to 6 ㎛, preferably 0.02 to 3.0 ㎛ can be applied. In the case of the antimony pentoxide, 50% particle size of 0.01 to 1.0 μm, preferably 0.02 to 0.5 μm may be applied. The antimony oxide may be used in an amount of 1 to 10 parts by weight, preferably 2.5 to 7 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the antimony oxide is used in excess of 10 parts by weight, it may impair the balance of physical properties of the resin.

The thermoplastic resin composition of the present invention may contain plasticizers, heat stabilizers, anti-drip agents, antioxidants, compatibilizers, light stabilizers, mold release agents, lubricants, impact modifiers, coupling agents, antistatic agents, dispersants, weather stabilizers, pigments, dyes, and inorganic materials, if necessary. It may further include additives such as additives. These may be used alone or in combination of two or more. 0.01 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin can be used. Examples of the inorganic additives include glass fibers, talc, ceramics and sulfates, but are not necessarily limited thereto.

The resin composition of the present invention may be prepared in pellet form by mixing the components and optionally additives at the same time and then melt extruding in an extruder. The prepared pellets may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding.

Another aspect of the present invention provides a molded article molded of the resin composition. In embodiments the molded article has a flame retardancy of 1/8 "thick V-1 or V-0 according to UL94 VB.

The molded article according to the present invention has excellent mechanical properties and excellent flame retardancy, so that not only daily miscellaneous goods, but also automobile parts, precision machine parts, structural materials, various interior accessories, TVs, computers, audio, air conditioners, exterior materials, computer housings, etc. Or other office equipment housings.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specification of the components used in Examples 1-9 and Comparative Examples 1-6 is as follows.

(A) thermoplastic resin

(a1) HIPS: Cheil Industries Co., Ltd. High Gloss HIPS Resin (HG-1760S) was used.

(a2) ABS: Cheil Industries Co., Ltd. g-ABS (CHT) was used.

(a3) Polyphenylene ether (PPE) resin: The poly (2, 6- dimethyl- phenyl ether) (brand name: S-202) of Asahi Kasehi, Japan was used.

(a4) Polycarbonate (PC) resin: PANLITE L-1250WP of TEIJIN, Japan, which is a bisphenol-A type linear polycarbonate resin having a weight average molecular weight of 25,000 g / mol, was used.

(B) selenium flame retardant

(b1) selenium-based flame retardant: A diphenyl diselenide product of Aldrich, USA was used.

(b2) selenium-based flame retardant: A dibenzyl diselenide product of Aldrich, USA was used.

(C) Phosphorus-based compound: Bis (dimethylphenyl) phosphate bisphenol A (trade name: CR741S) of Nippon-Defal Chemical was used.

Examples 1-9 and Comparative Examples 1-6

The pellets were prepared by extruding the above components in a temperature range of 200 to 280 ° C. in a conventional twin screw extruder according to the contents shown in Table 1 below. The prepared pellets were dried at 80 ° C. for 2 hours and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180˜260 ° C. and a mold temperature of 40˜80 ° C. to prepare a flame retardant specimen. The prepared specimens were measured for flame retardancy and total combustion time at a thickness of 1/8 "according to UL 94 VB flame retardant regulations. The measurement results are shown in Table 1 below.

From the results of Table 1, it can be seen that Examples 1 to 9 to which the selenium-based compound is applied as the flame retardant in the present invention have superior flame retardancy compared to Comparative Examples 1 to 6 using the phosphorus-based compound as the flame retardant.

According to the present invention, by applying environmentally friendly selenium compound as a new flame retardant instead of halogen-based flame retardants or phosphorus-based flame retardants with limited compatibility, the flame retardant effect is excellent compared to the use of conventional flame retardants. Has the effect of providing an flame retardant thermoplastic resin composition having a.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications are considered to be included within the scope of the present invention.

Claims (8)

(A) 100 parts by weight of thermoplastic resin and (B) 0.1 to 40 parts by weight of selenium-based flame retardant Including, The selenium-based flame retardant (B) is a flame retardant thermoplastic resin composition, characterized in that represented by the following formula (2): [Formula 2]

Wherein R ₁ and R ₂ are each independently a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₂₀ aryl group or a C ₆ -C ₂₀ aryl group substituted with a C ₁ -C ₁₀ alkyl group. The method of claim 1, wherein the thermoplastic resin (A) is aromatic vinyl resin, rubber modified aromatic vinyl resin, polyphenylene ether resin, polycarbonate resin, polyester resin, methacrylate resin, polyaryl A flame retardant thermoplastic resin composition selected from the group consisting of rensulfide-based resins, polyamide-based resins, polyvinyl chloride-based resins, poly-olipine-based resins, and mixtures thereof. The flame retardant thermoplastic resin composition according to claim 2, wherein the thermoplastic resin (A) is composed of 50 to 99% by weight of an aromatic vinyl resin and 1 to 50% by weight of a polyphenylene ether resin. The flame retardant thermoplastic resin composition according to claim 2, wherein the thermoplastic resin (A) is composed of 0 to 70% by weight of a rubber-modified aromatic vinyl resin and 30 to 100% by weight of a polycarbonate resin. delete The method of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of flame retardant, plasticizer, heat stabilizer, anti-dropping agent, antioxidant, compatibilizer, light stabilizer, pigment, dye, inorganic additives and mixtures thereof. Non-halogen flame-retardant polycarbonate resin composition, characterized in that. The molded article which shape | molded the flame-retardant thermoplastic resin composition of any one of Claims 1-4. The molded article according to claim 7, which is produced by extruding a flame retardant thermoplastic resin composition and has a flame retardancy of 1/8 "thick according to UL94 VB.