JP6941726B1 - Styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent thermal stability and weather resistance while maintaining excellent flame retardancy and mechanical properties (impact resistance) and a molded product thereof. SOLUTION: 51 to 99 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin are added to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. A styrene-based resin composition containing 1 to 49 parts by mass and further containing 0.01 to 6 parts by mass of (C) a zinc-based stabilizer. [Selection diagram] None

Description

The present invention relates to a styrene resin composition and a molded product thereof.

Since the styrene resin composition has excellent mechanical properties, it is widely used in housings for electric devices and electronic devices. However, since styrene resin is flammable, it cannot be used depending on the application.

Halogen-based flame retardants are particularly useful and often used to make styrene-based resins flame-retardant. However, halogen-based flame retardants are unstable at high temperatures and tend to decompose and deteriorate (color).

In order to prevent coloring by halogen-based flame retardants, for example, in Patent Document 1, by blending chlorinated polyethylene and organic tin-based stabilizer with styrene-based resin, it is excellent in flame retardancy and mechanical properties, and at the time of molding. A technique for reducing retention deterioration is disclosed.

Japanese Unexamined Patent Publication No. 63-108067

However, some organotins are regulated by REACH in Europe and their use is restricted. Therefore, there is a demand for a stabilized halogen-containing resin composition that does not use an organic tin stabilizer.

With the conventional technology, it is not possible to satisfy the thermal stability and weather resistance while maintaining the flame retardancy and mechanical properties of the styrene resin, and there is room for improvement.

An object to be solved by the present invention is to provide a resin composition and a molded product thereof having excellent thermal stability and weather resistance while maintaining excellent flame retardancy and mechanical properties (impact resistance). ..

The present inventors have diligently studied to solve the above problems. As a result, they have found that the above problems can be solved by adding a chlorine-based resin and a zinc-based stabilizer to the styrene-based copolymer, and have completed the present invention.

That is, the present invention is as follows.
[1]
51-99 parts by mass of (A) styrene-based copolymer and 1-49 parts by mass of (B) chlorine-based resin with respect to 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin in total. A styrene-based resin composition containing 0.01 to 6 parts by mass of (C) a zinc-based stabilizer.
[2]
The styrene-based resin according to [1], which further contains 0.01 to 6 parts by mass of (D) hydrotalcite with respect to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. Composition.
[3]
The (A) styrene-based copolymer contains the (A-1) rubbery polymer, and contains
The content of the rubbery polymer (A-1) is 2.5 to 40 parts by mass with respect to 100 parts by mass in total of the (A) styrene-based copolymer and (B) chlorine-based resin [1]. ] Or the styrene-based resin composition according to [2].
[4]
The (A-1) rubbery polymer is at least one selected from the group consisting of acrylonitrile-styrene-butadiene resin (ABS resin) and methyl methacrylate-butadiene-styrene resin (MBS resin) [3]. The styrene resin composition according to.
[5]
The styrene-based resin according to any one of [1] to [4], wherein the chlorinated resin (B) is at least one component selected from the group consisting of vinyl chloride resin (PVC resin) and chlorinated polyethylene (CPE). Resin composition.
[6]
The mass ratio of the (C) zinc-based stabilizer to the (D) hydrotalcite ((C) zinc-based stabilizer: (D) hydrotalcite) is 2: 8 to 7: 3, [2]. The styrene resin composition according to.
[7]
Any of [1] to [6] containing 0.01 to 5 parts by mass of (F) phosphite with respect to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. The styrene resin composition according to.
[8]
Described in any one of [1] to [7], which further contains 1 to 10 parts by mass of (G) antimony oxide with respect to a total of 100 parts by mass of the styrene-based copolymer (A) and the (B) chlorine-based resin. Styrene-based resin composition.
[9]
Any of [1] to [8], which further contains 0.1 to 5 parts by mass of (H) an ultraviolet absorber with respect to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. The styrene-based resin composition described in chlorine.
[10]
A molded product containing the styrene-based resin composition according to any one of [1] to [9].

According to the present invention, it is possible to provide a resin composition having excellent thermal stability and weather resistance while maintaining excellent flame retardancy and impact resistance, and a molded product thereof.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as embodiments) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following contents. The present invention can be implemented with various modifications within the scope of the gist thereof.

[Resin composition]
The styrene-based resin composition (hereinafter, also simply referred to as “resin composition”) in the present embodiment is (A) when the total of (A) styrene-based copolymer and (B) chlorine-based resin is 100 parts by mass. It contains 51 to 99 parts by mass of a styrene-based copolymer, 1 to 49 parts by mass of (B) a chlorine-based resin, and 0.01 to 6 parts by mass of (C) a zinc-based stabilizer. Hereinafter, the standard of the content of each component in the styrene resin composition of the present embodiment is set to 100 parts by mass in total of (A) styrene copolymer and (B) chlorine resin.

The lower limit of the content of the (A) styrene-based copolymer used in the present embodiment is preferably 55 parts by mass, more preferably 60 parts by mass, and the upper limit is preferably 95 parts by mass, more preferably 90 parts by mass. It is a mass part. When the content of the styrene-based copolymer (A) is 51 parts by mass or more, it is preferable from the viewpoint of thermal stability, and when it is 99 parts by mass or less, it is preferable from the viewpoint of flame retardancy.

The lower limit of the content of the chlorine-based resin (B) used in the present embodiment is preferably 5 parts by mass, more preferably 10 parts by mass, and the upper limit is preferably 46 parts by mass, more preferably 40 parts by mass. Is. The content of the chlorine-based resin (B) is preferably 1 part by mass or more from the viewpoint of flame retardancy, and preferably 49 parts by mass or less from the viewpoint of thermal stability.

The content of the zinc-based stabilizer (C) used in the present embodiment is 0.01 to 6 parts by mass, preferably 0.1 to 6 parts by mass, and more preferably 0.1 to 3 parts by mass. be. The content of the zinc-based stabilizer (C) is preferably 0.01 parts by mass or more from the viewpoint of thermal stability, and preferably 6 parts by mass or less from the viewpoint of impact resistance.

[(A) Styrene-based copolymer]
The (A) styrene-based copolymer that can be used in the resin composition of the present embodiment will be described in detail.

The (A) styrene-based copolymer that can be used in the present embodiment is not particularly limited, but is at least selected from styrene (hereinafter, also referred to as “St”) and α-methylstyrene (hereinafter, also referred to as “αMeSt”). Examples thereof include a polymer composed of one type and a copolymerizable component. The styrene-based copolymer (A) may consist of two or more components. Specific examples of the styrene-based copolymer (A) are not particularly limited, but for example, St-acrylonitrile (hereinafter, also referred to as “AN”) copolymer, αMeSt-AN copolymer, and St-αMeSt-AN copolymer weight. There are coalescence, St-AN-maleimide-based copolymer, St-methylmethacrylate (hereinafter, also referred to as "MMA") copolymer, St-MMA-maleimide-based copolymer, St-maleic anhydride copolymer and the like. In addition to the above components, other vinyl monomers such as o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, bromstyrene, methacrylatelyl, chloroacrylonitrile, ethylmethacrylate, propylmethacrylate, propylmethacrylate, Similarly, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, which are further copolymerized by at most 10% by mass, can be used in the same manner.

The (A) styrene-based copolymer is preferably at least one selected from acrylonitrile / styrene resin and acrylonitrile / α-methylstyrene resin, and may be a mixture of two or more.

In the (A) styrene-based copolymer used in the present embodiment, the ratio of the styrene component is preferably 60 to 85% by mass. More preferably, it is 70 to 80% by mass.

The number average molecular weight of the (A) styrene-based copolymer used in the present embodiment is preferably 40,000 to 150,000. When the number average molecular weight is 40,000 or more, the mechanical strength tends to be maintained. Further, when the number average molecular weight is 150,000 or less, it tends to be possible to obtain a resin composition having excellent thermal stability and weather resistance and a molded product thereof.

The lower limit of the number average molecular weight is more preferably 45,000 or more, still more preferably 50,000 or more. The upper limit of the number average molecular weight is more preferably 135,000 or less, still more preferably 120,000 or less.

In this embodiment, the number average molecular weight of the (A) styrene-based copolymer can be measured by the following method. The (A) styrene-based copolymer is immersed in tetrahydrofuran (THF), and the dissolved (A) styrene-based copolymer component is filtered off. The obtained filtrate is used and measured by gel permeation chromatography (GPC). Based on the measurement result, the number average molecular weight of the (A) styrene-based copolymer is calculated using polystyrene (PS) as a standard substance.

Further, the (A) styrene-based copolymer used in the present embodiment preferably contains (A-1) a rubbery polymer. Specific examples of the rubbery polymer (A-1) are not particularly limited, but for example, acrylonitrile-styrene-butadiene resin (a copolymer of acrylonitrile, styrene and butadiene, hereinafter also referred to as "ABS resin"), methacryl. Examples thereof include methyl butadiene styrene resin (a copolymer of methyl methacrylate, butadiene and styrene, hereinafter also referred to as “MBS resin”). The rubbery polymer (A-1) may be used alone or in a mixture of two or more kinds. In the resin composition of the present embodiment, the content of the (A-1) rubbery polymer is 2.5 with respect to a total of 100 parts by mass of the (A) styrene-based copolymer and (B) chlorine-based resin. It is preferably about 40 parts by mass. More preferably, it is 5 to 35 parts by mass, and further preferably 5 to 30 parts by mass. The content of the rubbery polymer (A-1) is preferably 2.5 parts by mass or more from the viewpoint of impact resistance, and 40 parts by mass or less is preferable from the viewpoint of weather resistance.

The average rubber particle size of the (A-1) rubbery polymer is preferably 0.1 to 1.0 μm, more preferably 0.1 to 0.5 μm.

[(B) Chlorine-based resin]
The (B) chlorine-based resin that can be used in the resin composition of the present embodiment will be described in detail.

The (B) chlorinated resin that can be used in the present embodiment is not particularly limited, and is selected from, for example, chlorinated polyethylene, polyvinyl chloride (vinyl chloride resin), polyvinylidene chloride, chlorinated polypropylene, and chlorinated vinyl chloride. At least one kind is mentioned, and two or more kinds may be mixed. Above all, the chlorinated resin (B) is preferably at least one component selected from the group consisting of vinyl chloride resin (PVC resin) and chlorinated polyethylene (CPE).

The chlorinated polyethylene (hereinafter, also referred to as “CPE”) is produced, for example, by chlorinating the polyethylene powder or particles described below in an aqueous suspension, or by dissolving polyethylene in an organic solvent and chlorinating it. can do. Of these, the method of chlorinating in an aqueous suspension is preferable. CPE is industrially manufactured and used in various fields, and the above-mentioned manufacturing method and various physical characteristics are well known.

The raw material polyethylene is homopolymerized with ethylene or copolymerized with ethylene at most 20% by mass (preferably 10% by mass or less) and at most 12 (preferably 3 to 8) α-olefins. It is obtained by doing. The density of the polyethylene is preferably generally is 0.910~0.970g / cm ^3, more preferably especially 0.920~0.970g / cm ^3.

The chlorine content of the CPE used in this embodiment is preferably 10 to 45% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 40% by mass. When the chlorine content of CPE is 10% by mass or more, the impact resistance and flame retardancy of the obtained resin composition tend to be excellent. Further, when the chlorine content of CPE is 45% by mass or less, the obtained resin composition tends to be excellent not only in impact resistance but also in thermal stability. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of CPE is generally preferably 30 to 150, more preferably 40 to 150, and even more preferably 40 to 130. When the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of CPE is 30 or more, the mechanical strength of the obtained resin composition tends to be high. Further, it is preferable that the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of CPE is 150 or less in terms of moldability.

As the polyvinyl chloride (hereinafter, also referred to as "PVC"), PVC having a degree of polymerization in the range of 400 to 4500 is preferable. More preferably, PVC is in the range of 400-3000.

Further, the chlorinated resin (B) is a copolymer of chlorinated polyethylene, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene and a compound having at least one double bond capable of copolymerizing with these. You may. Specific examples of the copolymer are not particularly limited, but for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, and the like. Vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chloride Vinyl-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer , Vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, plasticized polyvinyl chloride.

PVC is a polymer produced by homopolymerizing vinyl chloride or copolymerizing other types of monomers that can be copolymerized with vinyl chloride. Typical examples of other types of monomers include vinylidene chloride, ethylene, vinyl acetate, acrylonitrile, acrylic acid, methacrylic acid and maleic anhydride, and esters thereof. The copolymerization ratio of other types of monomers is usually preferably at most 40% by mass, and more preferably 30% by mass or less.

These homopolymers and copolymers are generally produced by suspension polymerization, bulk polymerization or emulsion polymerization. The average degree of polymerization of PVC used in the present embodiment is generally preferably 400 to 2,000 from the viewpoint of kneadability in producing the composition, mechanical properties of the obtained composition, and thermal stability. , 400 to 1,800 are more preferable, and 400 to 1,600 is particularly preferable. When the average degree of polymerization of PVC is 400 or more, the obtained resin composition is excellent in impact resistance. Further, when the average degree of polymerization of PVC is 2,000 or less, it is excellent in terms of moldability. These PVCs are industrially manufactured and used in various fields, and their manufacturing methods and physical properties are well known.

[(C) Zinc stabilizer]
The zinc-based stabilizer (C) that can be used in the present embodiment is not particularly limited, and examples thereof include an organic acid zinc salt. The organic acid constituting the metal salt of the organic acid is not particularly limited, and examples thereof include organic carboxylic acids and phenols. It is preferably an organic carboxylic acid. The organic carboxylic acid constituting the zinc salt of organic carboxylic acid is not particularly limited as an example of the carboxylic acid, but for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, neooctanoic acid, and the like. 2-Ethylhexic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 2-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid , P-tert-butyl benzoic acid, dimethyl hydroxy benzoic acid, 3,5-ditert-butyl-4-hydroxy benzoic acid, toluic acid, dimethyl benzoic acid, ethyl benzoic acid, cumic acid, n-propyl benzoic acid, amino Asbestosic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, P-tert-octylsalicylic acid, oleic acid, ellaic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid, etc. Monovalent carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebatic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorphthalic acid, aminophthalic acid , Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, monoesters of divalent carboxylic acids such as thiodipropionic acid or monoamide compounds, hemimeric acid, trimeric acid, merofuanic acid, pyromeritic acid and the like. Di or triester compounds of valent or tetravalent carboxylic acids can be mentioned.

Examples of the above-mentioned phenols are not particularly limited, but for example, tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, etc. Isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamilphenol, methylisohexylphenol, methyl-tert-octylphenol And so on.

The content of (C) zinc-based stabilizer (for example, zinc salts of these organic carboxylic acids) is 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. 6 parts by mass. The content of the zinc-based stabilizer (C) is preferably 0.1 to 6 parts by mass, more preferably 0.1 to 3 parts by mass. The content of the zinc-based stabilizer (C) is preferably 6 parts by mass or less from the viewpoint of impact resistance, and preferably 0.01 parts by mass or more from the viewpoint of heat resistance.

[(D) Hydrotalcite]
The resin composition of the present embodiment preferably further contains (D) hydrotalcite.

The content of (D) hydrotalcite is preferably 0.01 to 6 parts by mass, more preferably 0. It is 1 to 5 parts by mass, particularly preferably 0.1 to 3 parts by mass. When the content of (D) hydrotalcite is in such a range, thermal stability can be improved.

Examples of the (D) hydrotalcite used in the present embodiment include compounds represented by the following general formula (I).

Mg _1-x Al _x (OH) ₂ A _{x / 2} · mH ₂ O (I)
(Wherein, x is a real number in the range of 0 <x ≦ 0.5, A represents a CO ₃ or SО _4, m represents a real number.)

It is thermally stable that the mass ratio of the (C) zinc-based stabilizer to the (D) hydrotalcite ((C) zinc-based stabilizer: (D) hydrotalcite) is 2: 8 to 7: 3. It is preferable from the viewpoint of sex, and more preferably 2: 8 to 6: 4.

[(E) Rubber polymer]
The resin composition of the present embodiment may contain (E) a rubbery polymer other than (A-1) a rubbery polymer. The content of the rubbery polymer (E) is preferably 2.5 to 40 parts by mass, more preferably 2.5 to 40 parts by mass, based on 100 parts by mass of the total of the (A) styrene copolymer and the (B) chlorine-based resin. , 5 to 35 parts by mass, more preferably 5 to 30 parts by mass. When the content of the rubber polymer (E) is 2.5 parts by mass or more, it is preferable from the viewpoint of impact resistance, and when it is 40 parts by mass or less, it is preferable from the viewpoint of weather resistance.

Further, the rubbery polymer (E) is at least one selected from the group consisting of a silicone resin, ethylene / propylene / diene rubber (copolymer rubber of ethylene, propylene and diene) and an acrylic copolymer. preferable.

The average rubber particle size of the rubbery polymer (E) is preferably 0.1 to 1.0 μm, more preferably 0.1 to 0.5 μm.

[Manufacturing method of rubber polymer]
The method for producing (A-1) rubbery polymer and (E) rubbery polymer (hereinafter, also simply referred to as “rubbery polymer”) that can be used in the resin composition of the present embodiment will be described in detail. explain.

The method for producing the rubbery polymer that can be used in the present embodiment is not particularly limited, and examples thereof include a method obtained by grafting (e2) a graft resin on the (e1) rubber component.

(E1) The rubber component is not particularly limited, and is, for example, butadiene rubber, butadiene / styrene rubber (polymer rubber of butadiene and styrene), acrylic rubber, silicon / acrylic rubber (polymer rubber of silicon and acrylic). ), At least one selected from. The (e2) graft resin is not particularly limited, and examples thereof include a graft resin composed of at least one selected from (e2-1) styrene resin and (e2-2) acrylic resin.

The styrene-based resin (e2-1) is not particularly limited, and examples thereof include at least one selected from styrene and α-methylstyrene, and a styrene-based resin obtained by copolymerizing a copolymerizable component thereof may be used. The copolymerizable component is not particularly limited, and examples thereof include acrylonitrile and meta-acrylonitrile.

Specific examples of the rubbery polymer are not particularly limited, but for example, a butadiene homopolymerized rubber and a butadiene type selected from a random or block copolymerized rubber of butadiene and a small amount (generally 40% by mass or less) of styrene or acrylonitrile. Rubber is mentioned. The copolymer component may consist of two or more kinds. It is preferably at least one selected from acrylonitrile / styrene resin and acrylonitrile / α-methylstyrene resin, and may be a mixture of two or more, and more preferably (A-1) other than the rubbery polymer (A-1). ) Consists of the same components as the styrene copolymer.

The acrylic resin (e2-2) is not particularly limited, but is, for example, an acrylic acid ester (for example, butyl acrylate) or a small amount (generally 10% by mass or less) of the ester and other monomers (for example, 10% by mass or less). Examples thereof include acrylic acid ester-based rubber obtained by polymerizing with acrylonitrile). Specific examples of the (e2-2) acrylic resin are not particularly limited, but are, for example, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; Acrylic acids such as (meth) acrylic acid; may be mentioned, and these may be used alone or in combination of two or more.

Other rubbery polymers include a copolymerized rubber of ethylene and propylene, and a linear or branched diene containing two double bonds of ethylene and propylene and a small amount (generally 10% by mass or less) at the end. Olefins (eg 1.4-pentadiene), linear or branched diolefins with only one double bond at the end (eg 1.4-hexadiene) and bicyclo (2,2,1) -hebutene- Examples thereof include ethylene-propylene-based rubbers selected from multi-element copolymerized rubbers of 2 or its derivatives.

[(F) Phosphite]
The resin composition of the present embodiment preferably further contains (F) phosphite.

The content of (F) phosphite is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of (A) styrene copolymer and (B) chlorine resin. 3 parts by mass. When the content of (F) phosphite is in such a range, high thermal stability can be achieved.

Examples of the above-mentioned phosphite are not particularly limited, but for example, diphenyldecylphosphite, triphenylphosphite, tris-nonylphenylphosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, and tributylphos. Fight, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis (neohentyl cricol) -1,4-cyclohexanedimethylphosphite, Distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenylacid phosphite, tris (lauryl-2-thioethane) phosphite, tetratridecyl-1,1,3-) squirrel (2-methyl-5- 6th Butyl-4-oxyphenyl) Butane Diphosphite, Tetra (C12-C15 Mixed Alkyl) 4,4-Inglobilidenediphenyl Diphosphite, Tris (4-oxy-2,5-di-5th Butylphenyl) ) Phosphite, Tris (4-oxy-3,5-di-6th butylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, Tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4, 4-Isopropyridene diphenol polyphosphite, diphenyl-bis [4,5-n-butylidenebis (2-third butyl-5-methylphenol)] thiojetanol diphosphite, bis (octylphenyl) bis [4 , 4-n-Butylidenebis (2-5th Butyl-5-Methylphenol)] -1,6-Hexanediol diphosphite, phenyl-4,4-inglopyridenediphenol pentaerythritol diphosphite, phenyldiisodecylphos Examples thereof include phyto, tetratritesyl-4,4'-n-butyritenebis (2-6th butyl-5-methylphenol) diphosphite, and tris (2,4-di-3th butylphenyl) phosphite.

[(G) Antimony oxide]
The resin composition of the present embodiment preferably further contains (G) antimony oxide.

The content of (G) antimony oxide is preferably 1 to 10 parts by mass, more preferably 3 to 9 parts by mass, based on 100 parts by mass of the total of (A) styrene copolymer and (B) chlorine resin. be. When the content of (G) antimony oxide is in such a range, high flame retardancy and stabilization of flame retardancy can be achieved. (G) Antimony oxide is widely used as a flame retardant aid. The (G) antimony oxide is not particularly limited, and examples thereof include antimony oxides such as antimony trioxide (antimony trioxide) and antimony pentoxide. The average particle size of the antimony oxide is preferably 0.3 to 150 μm.

[(H) UV absorber]
It is preferable that the resin composition of the present embodiment further contains (H) an ultraviolet absorber.

The content of the ultraviolet absorber (H) is preferably 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total of the (A) styrene-based polymer and (B) chlorine-based resin. Parts are more preferable, and more preferably 0.1 to 2 parts by mass. (H) When the content of the ultraviolet absorber is in such a range, the stability at the time of molding (particularly the stability at heat retention) is improved while maintaining the mechanical properties, and the molded product has good gloss. Can be obtained.

The ultraviolet absorber (H) is not particularly limited, and examples thereof include benzophenone type, benzotriazole type, salicylate type, substituted acrylonitrile type, various metal salts or metal chelate, triazine type, piperidine type and the like. Specific examples of the (H) ultraviolet absorber are not particularly limited, and examples thereof include 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.

[Other ingredients]
Known additives can be added to the resin composition of the present embodiment as long as the object of the present invention is not impaired. The additive is not particularly limited, but is, for example, a flow modifier (silicon oil, polyethylene wax, aliphatic alcohol, ethylene bisstearic acid amide, etc.), a filler (talc, mica, calcium carbonate, etc.). , Conductivity-imparting agents (carbon black, carbon nanotubes, graphite, etc.), colorants (titanium oxide, zinc oxide, iron oxide, aluminum oxide, organic dyes, etc.), weather resistant agents, lubricants, antioxidants, etc. The content of these is preferably 30 parts by mass or less for the filler and the conductivity-imparting agent, and 5 parts by mass or less for the other parts, with respect to 100 parts by mass in total of the (A) styrene copolymer and (B) chlorine-based resin. Is. These may be used alone or in combination of two or more.

[Manufacturing method of resin composition]
The resin composition of the present embodiment can be produced by a known method. Specifically, although not particularly limited, it is produced by mixing, melt-kneading, and molding the raw material components as follows by, for example, a uniaxial or multi-screw kneading extruder, a roll, a Banbury mixer, a pressure kneader, or the like. be able to.

The method of mixing and melt-kneading the raw material components is not particularly limited, and a method well known to those skilled in the art can be used. Specifically, although not particularly limited, for example, a method in which the raw material components are mixed in advance with a super mixer, a tumbler, a V-shaped blender, or the like, and batch melt-kneaded with a single-screw extruder or a twin-screw extruder, and some components are used. Examples thereof include a method of adding components remaining from the middle of the extruder while supplying the twin-screw extruder to the main throat portion and melt-kneading the mixture. Any of these can be used, but in order to improve the mechanical characteristics of the molded product of the present embodiment, (B) a non-chlorine resin other than the chlorine-based resin is supplied to the main throat portion of the twin-screw extruder and melt-kneaded while being melt-kneaded. The method of adding the (B) chlorine-based resin from the middle is preferable. Since the optimum conditions vary depending on the size of the extruder, it is preferable to appropriately adjust the conditions within a range that can be adjusted by those skilled in the art. More preferably, the screw design of the extruder is also adjusted in various ways within a range that can be adjusted by those skilled in the art.

[Molded product]
The molded product in this embodiment contains the above-mentioned styrene resin composition.

[Manufacturing method of molded product]
The molding method for obtaining the molded product in the present embodiment is not particularly limited, and a known molding method can be used. Specifically, but not particularly limited, for example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, molding of other materials, gas-assisted injection molding, foam injection molding, low-pressure molding, ultra-thin. It can be molded by any of molding methods such as meat injection molding (ultra-high-speed injection molding) and in-mold composite molding (insert molding, outsert molding).

[Use]
The resin composition of the present embodiment can be used as a raw material for a molded product that requires flame retardancy, mechanical strength, and appearance.

The molded body of the present embodiment can be suitably used as a housing for electric devices and electronic devices, and can be particularly suitably used for electronic devices for indoor and outdoor applications, exteriors of electric and gas meters, parts of fire alarms, and the like.

Hereinafter, the present embodiment will be specifically described with reference to Examples and Comparative Examples, but the present embodiment is not limited to these Examples and Comparative Examples as long as the gist thereof is not exceeded.

The production conditions and evaluation items of the resin composition and the molded product used in Examples and Comparative Examples are as follows.

(1) Extrusion The raw materials were collectively blended and extruded with a twin-screw machine (ZSK-25) in which the cylinder temperature was set to 160 to 200 ° C. to obtain a resin composition.

(2) Preparation of molded product Resin of a small test piece conforming to JIS K7152-1 and ISO 294-1 from the resin composition obtained by using an injection molding machine (EC-75SXII, manufactured by Toshiba Machine Co., Ltd.). A molded product was obtained. Further, as a test piece for a combustion test, a resin molded product of a small test piece conforming to IEC-60695-11-10 was obtained from the obtained resin composition.

(3) Flame retardancy test A combustion test was conducted using a resin molded body of a small test piece of 125 mm × 13 mm × 1.5 mm molded according to the IEC-60695-11-10, and the flame retardancy was determined as follows. It was evaluated as.
〇: (Pass) Self-extinguishing ×: (Fail) No self-extinguishing

(4) Impact resistance (Charpy impact strength)
Using a resin molded body of a small test piece molded in accordance with ISO294-1, a post-cutting impact strength test in accordance with ISO179 was performed, Charpy impact strength was measured, and impact resistance was evaluated as follows. ..
〇: (Pass) Charpy impact strength value 5 kJ / m ² or more ×: (Fail) Charpy impact strength value less than 5 ^{kJ / m 2}

(5) Thermal stability (heat retention stability)
The temperature of the molding machine was set to 200 ° C., and the thermal stability was evaluated as follows from the amount of silver generated in the sample molded after melting and staying in the molding machine for 10 minutes.
◎: (Pass) No silver 〇: (Pass) Silver is seen in less than 1/10 of the whole △: (Fail) Silver is seen in the range of 1/10 to 1/4 of the whole ×: (Fail) ) Silver is seen over 1/4 of the whole surface, which is very large

(6) Weather resistance Using a resin molded body of a small test piece molded in accordance with the ISO 294-1, a super xenon weather meter (SX75 manufactured by Suga Test Instruments Co., Ltd.) was used to perform a test at a temperature of 63 ° C. for 500 hours. It was evaluated as follows.
〇: (Pass) Weather-resistant discoloration ΔE = less than 27 ×: (Failure) Weather-resistant discoloration ΔE = 27 or more

[Ingredients]
The raw material components of the resin composition and the molded product used in Examples and Comparative Examples will be described below.

The following styrene-based copolymers (A) were used.
(A1) Acrylonitrile-styrene resin (AS resin): Acrylonitrile ratio 25% by mass, number average molecular weight 55,000
(A2) Acrylonitrile-styrene-butadiene resin (ABS resin): rubbery polymer, average rubber particle size 500 nm
In this example, the number average molecular weight of the (A) styrene-based copolymer was measured by the following method. The (A) styrene-based copolymer was immersed in tetrahydrofuran (THF), and the dissolved (A) styrene-based copolymer component was filtered off. The obtained filtrate was used and measured by gel permeation chromatography (GPC). Based on the measurement result, the number average molecular weight of the (A) styrene-based copolymer was calculated using polystyrene (PS) as a standard substance.

(B) The following chlorine-based resins were used.
(B1) Polyvinyl chloride (PVC resin): Average degree of polymerization 600
(B2) Chlorinated polyethylene (CPE): MFR 1.5 g / 10 min, chlorine content 30% by mass

(C) The following zinc-based stabilizers were used.
(C1) Zinc stearate: Zinc content 10% by mass

(D) The following hydrotalcites were used.
(D1) Hydrotalcite: Mg _1-x Al _x (OH) ₂ A _{x / 2} · mH ₂ O (I)
(Wherein, x is a real number in the range of 0 <x ≦ 0.5, A represents a CO ₃ or SО _4, m represents a real number.)

(F) The following phosphite was used.
(F1) Phosphite: Tris (2,4-di-3 butylphenyl) phosphite

The following antimony oxide was used as (G) antimony oxide.
(G1) Antimony trioxide: Average particle size 1 μm

(H) The following UV absorbers were used.
(H1) UV absorber: 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole

(I) Organic tin stabilizers (I1) Dibutyl tin malate and dioctyl tin malate

[Example 1 , Reference Examples 1 to 9 , Comparative Examples 1 to 5]
Raw materials were blended so that each component had a ratio shown in Table 1 and extruded by the above method to produce a resin composition. Using the obtained resin composition, molding was carried out under the above conditions to produce a molded product.
The physical characteristics of the obtained molded product were measured by the above method, and the results are summarized in Table 1.
From the results of the above Examples and Comparative Examples, it is clear that the resin composition of the present embodiment is excellent in flame retardancy, impact resistance, thermal stability, and weather resistance.

Since the resin composition and the molded product of the present invention are excellent in thermal stability and weather resistance while maintaining excellent flame retardancy and impact resistance, they are industrially used in the fields of housings of electric devices and electronic devices. Has the availability of.

Claims (9)

51-99 parts by mass of (A) styrene-based copolymer and 1-49 parts by mass of (B) chlorine-based resin with respect to 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin in total. Styrene-based resin composition containing 0.01 to 6 parts by mass of (C) zinc-based stabilizer and 0.1 to 5 parts by mass of (H) ultraviolet absorber (however, those containing an organic tin stabilizer). And those containing magnesium hydroxide). The styrene-based resin according to claim 1, further containing 0.01 to 6 parts by mass of (D) hydrotalcite with respect to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. Composition. The (A) styrene-based copolymer contains the (A-1) rubbery polymer, and contains
The claim that the content of the rubbery polymer (A-1) is 2.5 to 40 parts by mass with respect to 100 parts by mass in total of the (A) styrene-based copolymer and (B) chlorine-based resin. The styrene-based resin composition according to 1 or 2. 3. The rubbery polymer (A-1) is at least one selected from the group consisting of acrylonitrile-styrene-butadiene resin (ABS resin) and methyl methacrylate-butadiene-styrene resin (MBS resin). The styrene resin composition according to. The styrene-based resin according to any one of claims 1 to 4, wherein the chlorinated resin (B) is at least one component selected from the group consisting of vinyl chloride resin (PVC resin) and chlorinated polyethylene (CPE). Resin composition. 2. The mass ratio of the (C) zinc-based stabilizer to the (D) hydrotalcite ((C) zinc-based stabilizer: (D) hydrotalcite) is 2: 8 to 7: 3. The styrene resin composition according to. Any one of claims 1 to 6, further containing 0.01 to 5 parts by mass of (F) phosphite with respect to a total of 100 parts by mass of (A) styrene-based copolymer and (B) chlorine-based resin. The styrene resin composition according to. The invention according to any one of claims 1 to 7, further comprising 1 to 10 parts by mass of (G) antimony oxide with respect to 100 parts by mass of the total of the styrene copolymer (A) and the chlorine resin (B). Styrene-based resin composition. A molded product containing the styrene-based resin composition according to any one of claims 1 to 8.