JPH11199750A - Compound for abs-pvc alloy, its pellet, and frame-retardant crate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound excellent in injection moldability and heat resistance, impact resistance, and weathering resistance as well by mixing a combination of a pelletized ABS resin with a powdery PVC resin in a specified ratio with specified amounts of an alkyl (meth)acrylate resin, a stabilizer, and a lubricant. SOLUTION: This compound is obtained by mixing a combination of 20-70 wt.% ABS resin with 80-30 wt.% PVC resin, per 100 pts.wt. PVC resin, 0.5-20 pts.wt. alkyl (meth)acrylate resin, 3-12 pts.wt. stabilizer, and 3-12 pts.wt. lubricant. The ABS resin used is one comprising 40-85 wt.% polymer prepared by bulk-polymerizing 15-35 wt.% vinyl cyanide compound, 85-65 wt.% aromatic vinyl compound, etc., and having a reduced viscosity of 0.20-0.55 dl/g and 60-15 wt.% polymer prepared by emulsion-polymerizing 60-15 wt.% monomer mixture comprising 15-35 wt.% vinyl cyanide compound, 85-65 wt.% aromatic vinyl compound, etc., in the presence of 40-85 wt.% diene rubber and having a rubber content of 10-40 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for an ABS-PVC alloy having excellent surface properties, weathering resistance, workability and flame retardancy, a pellet for injection molding comprising the compound, and a flame retardant housing. It is.

[0002]

2. Description of the Related Art ABS-PVC alloys composed of a low molecular weight ABS resin (a graft copolymer of acrylonitrile and styrene onto butadiene rubber and an acrylonitrile-styrene copolymer) and a vinyl chloride resin having a low degree of polymerization are widely used. Made of ABS resin and vinyl chloride resin
Unlike MBS-PVC resin consisting of BS-PVC resin, MBS resin (graft copolymer of butadiene rubber with methyl methacrylate and styrene) and vinyl chloride resin, it has excellent injection moldability, impact resistance, and heat deformation resistance. It is widely used especially for computer displays, copiers, facsimiles, housings of OA equipment such as telephones, housings of home electric appliances, etc. because of its weatherability, economical properties and the like.

However, in recent years, computer displays and the like have been required to be easy to view, like TVs, and have been increasing in size. In view of economy, the thickness of the housing has been decreasing. For this reason, ABS-PVC alloys are required to have better injection moldability. ABS-PVC
The injection moldability of alloys, particularly burns, black spots, and silver during injection molding, are greatly affected by the thermal decomposition of PVC. As a means for improving the thermal stability of PVC, a method of using a large amount of a stabilizer or a lubricant has conventionally been adopted. However, when a stabilizer and a lubricant are added in amounts exceeding conventional amounts, heat resistance, impact resistance and economic efficiency are reduced.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide an ABS-PVC alloy excellent in injection moldability, heat resistance, impact resistance, weather resistance and economy. It is assumed that.

[0005]

As the ABS resin used in the ABS-PVC alloy, a powder produced by an emulsion polymerization method has conventionally been used. However, we have:
It was considered that the ABS resin produced by emulsion polymerization has a large amount of auxiliary materials remaining, which may hinder the thermal stability of PVC.
In addition, when powdered ABS is used, a stabilizer that prevents thermal deterioration of PVC at the compounding stage is dispersed not only in PVC but also in ABS. Particularly, the dispersibility of the stabilizer in the compound is determined by extruding the compound into pellets. It was considered that plasticization during pelletization affects the initial degradation of PVC in the melting stage. The present inventors have conducted intensive studies in view of these points. As a result, the use of a specific pellet-shaped ABS resin and an alkyl (meth) acrylate resin provides excellent injection moldability, heat resistance, weather resistance, and impact resistance. The present inventors have found that an ABS-PVC alloy having excellent properties can be obtained, and have reached the present invention. That is, a first aspect of the present invention is a pellet-like ABS resin (I) shown below in an amount of 20 to 70% by weight.
And 80 to 30% by weight of a powdery PVC resin (II), and an alkyl (meth) acrylate resin (III) of 0.5 to 50% by weight based on 100 parts by weight of the PVC resin (II).
An ABS comprising 20 parts by weight, 3 to 12 parts by weight of a stabilizer (IV), and 3 to 12 parts by weight of a lubricant (V).
-Contain a compound for PVC alloy. (I) ABS resin in pellet form: 15 to 35% by weight of a vinyl cyanide compound, 85 to 65% by weight of an aromatic vinyl compound, and 0 to 20% by weight of another copolymerizable vinyl compound (100% by weight in total) Copolymer (A) 40-85 having a reduced viscosity of 0.20 to 0.55 dl / g, polymerized by a polymerization method.
15 to 35% by weight of a vinyl cyanide compound, 85 to 65% by weight of an aromatic vinyl compound, and 0 to 20% by weight of another copolymerizable vinyl compound with respect to 40% to 85% by weight of a diene rubber (R). % (Total 100% by weight) of a graft copolymer (B) obtained by emulsion polymerization of 60 to 15% by weight of a monomer mixture (M) of 60 to 15% by weight, and a rubber content of 10 to 40%. ABS resin pellets in weight%. (II) PVC resin: viscosity average degree of polymerization of 400 to 800,
A vinyl chloride polymer or copolymer containing 80% by weight or more of vinyl chloride. (III) Alkyl (meth) acrylate resin: 40 to 100% by weight of acrylic (meth) acrylate, 60 to 0% by weight of another copolymerizable monomer, and a reduced viscosity of 1.5
10 to 10 dl / g of the copolymer (C) and 20 to 100% by weight of the alkyl (meth) acrylate, 80 to 0% by weight of another copolymerizable monomer, and a reduced viscosity of 0.05 to 0.
At least one resin selected from the group consisting of 5 dl / g copolymer (D); (IV) Stabilizer: a stabilizer comprising 55 to 100% by weight of a tin stabilizer and 45 to 0% by weight of another stabilizer. (V) Lubricant: at least one lubricant selected from the group consisting of ester lubricants having 10 to 70 carbon atoms, amide lubricants having 10 to 70 carbon atoms, hydrocarbon lubricants, metal soap lubricants and fatty acid lubricants.

A second aspect of the present invention is an ABS-PVC alloy pellet for injection molding, which is obtained by melting and kneading the above-mentioned ABS-PVC alloy compound, and a third aspect of the present invention is the above-mentioned pellet. Each has a flame-retardant housing for OA equipment, office machines, electronic equipment, electric equipment, etc. having excellent surface properties, which is obtained by injection molding.

[0007] The ABS resin (I) in the form of pellets used in the present invention comprises copolymer (A) in an amount of 40 to 85% by weight, preferably 50 to 80% by weight, more preferably 53 to 78% by weight, and graft copolymer. Polymer (B) 60 to 15% by weight, preferably 50 to 20% by weight, more preferably 47 to 22% by weight
It is a resin consisting of% by weight. The copolymer (A) contains 15 to 35% by weight, preferably 20 to 3% by weight of a vinyl cyanide compound.
5% by weight, more preferably 22 to 30% by weight, aromatic vinyl compound 85 to 65% by weight, preferably 80 to 65% by weight, more preferably 78 to 70% by weight, other copolymerizable vinyl compound 0 to 0% 20% by weight, preferably 0-10
% By weight, more preferably 0 to 7% by weight (total 100% by weight), reduced viscosity 0.2 to 0.55 dl / g, preferably 0.25 to 0.5 dl / g, more preferably 0.28 to 0.5 dl / g.
0.48 dl / g of a copolymer produced by a bulk polymerization method.

When the amount of the vinyl cyanide compound is less than 15% by weight, heat resistance and impact resistance decrease, and when it exceeds 35% by weight, injection moldability, impact resistance and weather discoloration resistance decrease. If the amount of the aromatic vinyl compound is less than 65% by weight, the injection moldability and impact resistance are reduced, and if it exceeds 85% by weight, the heat resistance and impact resistance are reduced. If the amount of the other copolymerizable vinyl compound exceeds 20% by weight, the injection moldability, heat resistance, impact resistance, and weather discoloration resistance are reduced. The polymerization method of the copolymer (A) is particularly important. In the case of an emulsion polymerization method or a suspension polymerization method other than the bulk polymerization method, injection moldability, weather discoloration resistance, and economy are reduced.

The graft copolymer (B) is a vinylene cyanide compound of 15 to 35% by weight based on 40 to 85% by weight, preferably 50 to 80% by weight, more preferably 53 to 77% by weight of the diene rubber (R). % By weight, preferably 20-33
%, More preferably 22-30% by weight, aromatic vinyl compound 85-65% by weight, preferably 80-67% by weight, more preferably 78-70% by weight, other copolymerizable vinyl compounds 0-20. % By weight, preferably 0 to 10% by weight, more preferably 0 to 7% by weight (total 100% by weight), 60 to 15% by weight, preferably 50 to 20% by weight, more preferably 50 to 20% by weight. Is 47-23
It is a graft copolymer obtained by polymerizing by weight% by an emulsion polymerization method.

When the diene rubber (R) is less than 40% by weight, the impact resistance decreases, and when it exceeds 85% by weight, injection moldability, impact resistance and weather discoloration resistance decrease. If the monomer mixture (M) is less than 15% by weight, injection moldability, impact resistance,
The weathering discoloration resistance decreases, and if it exceeds 60% by weight, the impact resistance decreases. If the amount of the vinyl cyanide compound in the monomer mixture is less than 15% by weight, heat resistance and impact resistance are reduced, and if it exceeds 35% by weight, injection moldability, impact resistance and weather discoloration resistance are reduced. If the amount of the aromatic vinyl compound is less than 65% by weight, the injection moldability and impact resistance are reduced, and if it exceeds 85% by weight, the heat resistance and impact resistance are reduced. If the amount of the other copolymerizable vinyl compound exceeds 20% by weight, the injection moldability, heat resistance, impact resistance, and weather discoloration resistance are reduced. The graft copolymer (B) is produced by an emulsion polymerization method because the graft ratio is easily controlled. In terms of impact resistance and injection moldability,
The graft ratio of the graft copolymer (B) is such that the average particle size is 1
For a diene rubber having a diameter of 50 nm or more, the content is 15 to 80% by weight, preferably 20 to 70% by weight, and more preferably 25 to 65% by weight. For a diene rubber having an average particle size of less than 150 nm, the graft ratio is 20 to 90% by weight, preferably 2 to 90% by weight.
The content is 5 to 85% by weight, more preferably 30 to 80% by weight. If the graft ratio is less than 20% by weight, the impact resistance and the coloring properties are reduced, and if it exceeds 90% by weight, the processability tends to be reduced.

The rubber content in the ABS resin (I) in the form of a pellet is 10 to 40% by weight, preferably 13 to 35% by weight, more preferably 15 to 33% by weight. If the rubber content is less than 10% by weight, the impact resistance decreases, and if it exceeds 40% by weight, the injection moldability and heat resistance decrease.

Acrylonitrile, methacrylonitrile and the like are used as vinyl cyanide compounds in the copolymer (A), and styrene, α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chloromethyl and the like are used as aromatic vinyl compounds. Styrene, bromostyrene and the like can be mentioned. Examples of other copolymerizable vinyl compounds include esters of methacrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. And carbon number 1
Esters of 12 straight-chain or side-chain alcohols,
For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, and maleimide compounds such as phenylmaleimide, cyclohexylmaleimide, and butylmaleimide are exemplified. These may be used alone or in combination of two or more.

The diene rubber (R) in the graft copolymer (B) includes butadiene rubber, styrene-butadiene rubber, butadiene-butyl acrylate rubber and the like, and these may be used alone or in combination of two or more. In particular, polybutadiene rubber and / or styrene
Butadiene rubber is preferred, and from the viewpoint of impact resistance and injection moldability, the particle size (volume average particle size) is preferably 100 nm or more,
More preferably 130 nm or more, even more preferably 150 nm
It is preferable that the above-mentioned enlarged rubber is contained in an amount of preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably 20% by weight or more (based on polybutadiene rubber and / or styrene-butadiene rubber). Furthermore, polybutadiene rubber and / or styrene-butadiene rubber have a particle size of 150 to 1000 n from the viewpoint of impact resistance and injection moldability.
m, preferably 170-800 nm, more preferably 15
10 to 90% by weight, preferably 15 to 85% by weight, more preferably 20 to 80% by weight of an enlarged rubber of 0 to 1000 nm
And an unexpanded rubber having a particle size of 40 to 150 nm, preferably 50 to 140 nm, more preferably 55 to 135 nm, 90 to 10% by weight, preferably 85 to 15% by weight, more preferably 8%.
It is composed of 0 to 20% by weight.

As the enlarged rubber, a rubber produced by a known emulsion polymerization is prepared by using a latex of an alkyl (meth) acrylate polymer having a carboxyl group, an acidic substance such as hydrochloric acid, acetic acid, sulfuric acid, or an electrolyte such as sodium sulfate. An enlarged one is preferred, and an enlarged one using an alkyl (meth) acrylate-based polymer latex having a carboxyl group is more preferred from the viewpoint of particle size control and impact resistance. Unexpanded rubber is produced by known emulsion polymerization.

In the monomer mixture (M) of the graft copolymer (B), acrylonitrile, methacrylonitrile and the like are used as the vinyl cyanide compound, and styrene, α-methylstyrene, p-methyl styrene and the like are used as the aromatic vinyl compound. Examples include methylstyrene, p-isopropylstyrene, chlorostyrene, bromostyrene and the like. Other copolymerizable vinyl compounds include methacrylic acid and C1-C1.
Esters of alcohols having 2 straight-chain or side chains, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like, esters of acrylic acid and alcohols having a straight-chain or side chain having 1 to 12 carbon atoms, For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, and maleimide compounds such as phenylmaleimide, cyclohexylmaleimide, and butylmaleimide are exemplified. These may be used alone or in combination of two or more.

The graft copolymer (B) may be produced using any initiator, chain transfer agent and emulsifier. The initiator is a thermal decomposition initiator such as potassium persulfate,
Known initiators such as a redox initiator such as Fe-reducing agent-organic peroxide can be used. Known chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer and terpinolene can be used. Examples of the emulsifier include fatty acid metal salt-based emulsifiers such as sodium oleate, sodium palmitate, and sodium rosinate, metal sulfonic acid salts such as sodium dodecylbenzenesulfonate, sodium alkylsulfonate having 12 to 20 carbon atoms, and sodium dioctyl sulfosuccinate. A known emulsifier such as an emulsifier can be used. These may be used alone or in combination of two or more.

The PVC resin (II) used in the present invention comprises:
Viscosity average degree of polymerization 400 to 800, preferably 450 to 7
00, more preferably 470 to 650, and at least 80% by weight, preferably 90% by weight of vinyl chloride.
% By weight or more, more preferably 93% by weight or more of a vinyl chloride copolymer powder. Viscosity average polymerization degree 400
If it is less than 100, the impact resistance and heat resistance decrease, and if it exceeds 800, the injection moldability decreases. Examples of the vinyl chloride polymer and the vinyl chloride copolymer having a vinyl chloride content of 80% by weight or more include powders such as polyvinyl chloride, vinyl chloride-ethylene copolymer, and vinyl chloride-alkyl acrylate copolymer. The PVC resin (II) may be produced by using any polymerization method, initiator, chain transfer agent or emulsifier, but from the viewpoint of injection moldability, a suspension polymerization method is preferred.

The alkyl (meth) acrylate (III) used in the present invention is the following copolymer (C) or copolymer (D), which may be used alone or in combination of two or more. The copolymer (C) contains 40 to 100% by weight of alkyl (meth) acrylate, preferably 50 to 95% by weight, more preferably 55 to 90% by weight, and 60 to 0% by weight of another copolymerizable monomer. , Preferably 50 to 5% by weight, more preferably 45 to 10% by weight, and a reduced viscosity of 1.
It is a copolymer of 5 to 10 dl / g, preferably 1.8 to 9 dl / g, more preferably 2 to 8 dl / g. Further, a copolymer having a Tg of 50 to 150 ° C, preferably 60 to 140 ° C, more preferably 70 to 130 ° C is suitable. When the amount of the alkyl (meth) acrylate is less than 40% by weight, that is, when the amount of the other copolymerizable monomer exceeds 60% by weight, the injection moldability and the impact resistance are reduced. When the reduced viscosity is less than 1.5 dl / g or more than 10 dl / g, the injection moldability and impact resistance are reduced. If the Tg is less than 50 ° C, the injection moldability tends to decrease. If the Tg exceeds 150 ° C, the injection moldability and impact resistance tend to decrease.

The copolymer (D) contains 20 to 100% by weight of alkyl (meth) acrylate, preferably 25 to 10% by weight.
0% by weight, more preferably 30 to 95% by weight, and 80 to 0% by weight of another copolymerizable monomer, preferably 75 to 0% by weight.
% By weight, more preferably 70 to 5% by weight, and reduced viscosity of 0.05 to 0.5 dl / g, preferably 0.1 to 0.45%.
dl / g, more preferably 0.15 to 0.4 dl / g. Further, Tg is -80 to 70C, preferably-
A copolymer at 70 to 60C, more preferably -60 to 50C is suitable. 20 alkyl (meth) acrylates
When the amount is less than 80% by weight, that is, when the amount of the other copolymerizable monomer exceeds 80% by weight, the injection moldability and the impact resistance are reduced. If the reduced viscosity is less than 0.05 dl / g or more than 0.5 dl / g, the injection moldability decreases. If the Tg is less than -80 ° C, the heat resistance tends to decrease, and if it exceeds 70 ° C, the injection moldability and impact resistance tend to decrease.

Examples of the alkyl (meth) acrylate in the copolymer (C) and the copolymer (D) include esters of methacrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms, for example, methyl methacrylate, ethyl Methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, and the like are esters of acrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms, for example, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl,
Examples thereof include 2-ethylhexyl acrylate and glycidyl acrylate. Among these, acrylates and methacrylates having an alkyl group having 1 to 8 carbon atoms are preferable from an industrial viewpoint such as production stability and economic efficiency, and butyl acrylate, butyl methacrylate, methyl methacrylate, and glycidyl methacrylate are particularly preferable. preferable. These may be used alone or in combination of two or more.

Examples of the copolymerizable monomer include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chlorostyrene and bromostyrene. (Meth) acrylate derivatives having a polar functional group such as a vinyl group compound, (meth) acrylic acid and glycidyl (meth) acrylate, and maleimide compounds such as maleimide and N-phenylmaleimide. Also, allyl methacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, dicyclopentadiene (meth) acrylate, 1,3,5-
A small amount of a polyfunctional monomer having two or more polymerizable functional groups in a molecule such as triacryloylhexahydro-s-triazine can be used in a small amount of 5% by weight or less.
These may be used alone or in combination of two or more. Among these, acrylonitrile, styrene, α-methylstyrene, and glycidyl (meth) acrylate are preferable from the industrial viewpoint such as production stability and economic efficiency.

The copolymer (C) and the copolymer (D) may be prepared by using any polymerization method, initiator, chain transfer agent or surfactant, but they are emulsified from the viewpoint of injection moldability. Polymerization is preferred. Further, those produced using any initiator, chain transfer agent, and emulsifier may be used. Known initiators such as a thermal decomposition initiator such as potassium persulfate and a redox initiator such as Fe-reducing agent-organic peroxide can be used as the initiator. t-dodecyl mercaptan, n-
Dodecyl mercaptan, α-methylstyrene dimer,
Known chain transfer agents such as terpinolene can be used. Examples of the emulsifier include fatty acid metal salt-based emulsifiers such as sodium oleate, sodium palmitate, and sodium rosinate, metal sulfonic acid salts such as sodium dodecylbenzenesulfonate, sodium alkylsulfonate having 12 to 20 carbon atoms, and sodium dioctyl sulfosuccinate. A known emulsifier such as an emulsifier can be used.
These may be used alone or in combination of two or more.

The stabilizer (IV) used in the present invention comprises 55 to 100% by weight of tin stabilizer, preferably 65 to 100% by weight, more preferably 70 to 100% by weight, and 45 to 0% by weight of another stabilizer. , Preferably 35 to 0% by weight, more preferably 30 to 0% by weight. Examples of the tin stabilizer include known dialkyltin maleate-based stabilizers and dialkyltin mercaptide-based stabilizers used for vinyl chloride resins. For example, if the structural formula is R ₁ R ₂
Assuming that SnXY, R ₁ and R _{2 each} have 1 to 8 carbon atoms.
Alkyl group. X and Y are malate, 2-ethylhexyl malate, benzyl malate,
Thioglycolate, 2-ethylhexylthioglycolate, benzylthioglycolate, 2-ethylhexyl-
3-mercaptopropionate, benzyl-3-mercaptopropionate and the like can be mentioned. These may be used alone or in combination of two or more, and they may be in a number form. Other heat stabilizers include vinyl chloride resins, known hindered phenolic antioxidants used for styrene resins, fatty acid metal salts, epoxy stabilizers,
Examples include phosphorus-based stabilizers and alkaline earth metal oxides. These may be used alone or in combination of two or more.

From the viewpoint of injection moldability, particularly preferred as the tin stabilizer are the ratios of a malate tin stabilizer, a sulfur tin stabilizer, and a phenolic antioxidant having a molecular weight of 300 or more to the malate tin stabilizer 20. 80% by weight, 5-80% by weight of sulfur tin stabilizer, 3-40% by weight of phenolic antioxidant having a molecular weight of 300 or more (total 100% by weight)
belongs to. More preferably, 25 to 75% by weight of a malate tin stabilizer, 10 to 75% by weight of a sulfur tin stabilizer, and 5 to 35% of a phenolic antioxidant having a molecular weight of 300 or more.
% By weight (total 100% by weight). From the viewpoint of injection moldability, the liquid tin stabilizer in the ABS-PVC alloy compound is 10 to 90% by weight of the tin stabilizer in 100% by weight.
%, Preferably 15 to 85% by weight, more preferably 20 to 80% by weight, and the tin content in the compound is 0.2 to 2% by weight, preferably 0.3 to 1.7%.
%, More preferably 0.4 to 1.5% by weight.

The lubricant (V) used in the present invention includes:
C12-70 ester lubricant, C10-70
Amide-based lubricants, hydrocarbon-based lubricants, metal soap-based lubricants, fatty acid-based lubricants, and the like, and these can be used alone or in combination of two or more. From the viewpoint of injection moldability, a combination of two or more lubricants is preferred. From the viewpoint of injection moldability,
C12-C70 ester lubricant and / or C1
A lubricant in which the amide-based lubricant of 0 to 70 is 30% by weight or more is preferable. Examples of the ester lubricant having 12 to 70 carbon atoms include esters of higher fatty acids having 8 to 40 carbon atoms and alcohols having 2 to 30 carbon atoms. Examples of the alcohol having 2 to 30 carbon atoms include polyfunctional alcohols such as glycol, glycerin, trimethylolpropane, and pentaerythritol, and aliphatic alcohols. Examples of the amide-based lubricant include amides of higher fatty acids having 10 to 30 carbon atoms, bisamides having 10 to 50 carbon atoms and oligomers thereof. Examples of the hydrocarbon-based lubricant include liquid paraffin, polyethylene wax having a molecular weight of 300 to 3000, and oxidized polyethylene wax. Examples of the metal soap-based lubricant include C of higher fatty acids having 12 to 30 carbon atoms.
a, a metal salt such as Mg, Sn, and Pb. Examples of the fatty acid-based lubricant include higher fatty acids having 12 to 30 carbon atoms. These may be used alone or in combination of two or more.

The compound for ABS-PVC alloy of the present invention comprises 20 to 70% by weight, preferably 25 to 65% by weight, of pelletized ABS resin (I), and powdery ABS resin (I).
VC resin (II): 80 to 30% by weight, preferably 75 to 3%
5% by weight, and based on 100 parts by weight of the PVC resin (II), alkyl (meth) acrylate resin (III)
0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, 3 to 12 parts by weight of the stabilizer (IV), preferably 4 to 10 parts by weight,
And 3 to 12 parts by weight, preferably 5 to 11 parts by weight of the lubricant (V). When component (I) is less than 20% by weight, heat resistance is reduced, and when it exceeds 70% by weight, flame retardancy and impact resistance are reduced. The component (I) is added to 100 parts by weight of the component (II).
If II) is less than 0.5 part by weight, thermal stability is reduced and pelletization becomes difficult. If it exceeds 20 parts by weight, flame retardancy,
Impact resistance decreases. When the component (IV) is less than 3 parts by weight, the thermal stability is reduced. When the component (IV) is more than 12 parts by weight, heat resistance and impact resistance are reduced. When the component (V) is less than 3 parts by weight, injection moldability is reduced. However, if it exceeds 12 parts by weight, heat resistance and impact resistance are reduced.

In the compound of the present invention, commonly known additives such as a UV absorber, an antistatic agent and a pigment can be appropriately used as needed. In particular, benzophenone-based, benzotriazole-based ultraviolet absorbers, hindered amine-based stabilizers, and the like used in styrene-based resins are used to improve the performance of the composition according to the present invention as a molding resin. Can be. These ultraviolet absorbers and hindered amine stabilizers can be used alone or in combination of two or more. ABS-P of the present invention
The compound for VC alloy is the above AB pellet
S resin (I), PVC resin (II), alkyl (meth) acrylate resin (III), stabilizer (IV), lubricant (V),
Further, if necessary, additives such as various pigments may be added, and the mixture may be uniformly mixed with a blender such as Henschel or ribbon. The blending temperature is from 40 to 40 from the viewpoint of injection moldability.
The temperature is raised from room temperature to a temperature of 140 ° C, preferably 50 to 130 ° C, more preferably 55 to 125 ° C, and the temperature is cut. The blending time is 2 to 30 minutes, preferably 3 to 25 minutes, more preferably 4 to 20 minutes, including the temperature raising time, from the viewpoint of injection moldability. The cooling time may be provided separately.

The ABS-PVC alloy pellets are obtained by mixing the ABS-PVC alloy compound obtained as described above with a Banbury mixer, a roll mill, a single screw extruder,
It can be manufactured by kneading with a known melt kneader such as a shaft extruder. From the viewpoint of the injection moldability of the pellets, the resin temperature during melt-kneading is 160 to 230 ° C, preferably 170 to 230 ° C.
20 ° C, particularly preferably 180 to 210 ° C.

The flame-retardant housing made of ABS-PVC alloy is
The ABS-PVC alloy pellets obtained as described above can be molded and manufactured by a known injection molding machine.
In view of the appearance of the flame-retardant housing, the molding resin temperature is 170
To 230 ° C, preferably 180 to 220 ° C, particularly preferably 190 to 210 ° C. From the viewpoint of the appearance of the flame-retardant casing, the CR of the screw of the injection molding machine is 1.4 to 3.
0, preferably 1.6 to 2.8, more preferably 1.8
２2.6.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but these are merely examples, and the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” represent parts by weight and% by weight, respectively. Abbreviations described below represent the following substances, respectively. AN: acrylonitrile St: styrene αMSt: α-methylstyrene BA: butyl acrylate MMA: methyl methacrylate VC: vinyl chloride BMA: butyl methacrylate GMA: glycidyl methacrylate BR: polybutadiene rubber (mixture of 50/50 weight ratio of particle diameter 300 nm and 100 nm) SBR: Styrene-butadiene rubber (mixture of 70/30 weight ratio of 400 nm and 70 nm, average particle size 300 nm)

Examples 1 to 6, Comparative Examples 1 to 7 Production of ABS resin (I) in pellet form (1) Production of copolymer (A) Copolymers (A-1), (A-2) and (A-3) are prepared by a known bulk polymerization method (Described in Kaihei 7-278217)
Using monomers AN, St, αMSt in the ratios shown in Table 1, polymerization temperature of 120 ° C., initiator 2,2-bis (di-
Synthesized using (t-butylperoxycyclohexyl) propane. The copolymer (A-4) was synthesized by an emulsion polymerization method (Japanese Patent Application No. 8-260629) using a polymerization temperature of 65 ° C., a polymerization time of 9 hours, and 0.3 parts of cumene hydroperoxide as an initiator. . Copolymer (A-1),
(A-2) and (A-3) were obtained as pellets. The copolymer (A-4) was obtained as a latex. Table 1 shows the composition (parts) and reduced viscosity. (2) Production of graft copolymer (B) Graft copolymer (B-1), (B-2), (B-
3) and (B-4) are emulsion polymerization methods (Japanese Patent Application No. Hei 8-2606).
29), BR, SBR, AN, St, MMA, BA
At a polymerization temperature of 60 ° C., a polymerization time of 7 hours, and cumene hydroperoxide 0.1 as an initiator.
Parts (per 100 parts of monomer).
Table 1 shows the composition (parts), the graft ratio, and the particle size of the rubber polymer. (3) Production of ABS resin (I) 1) ABS resin (I-1), (I-2) in pellet form,
Production of (I-3) The above graft copolymer (B-1), (B-2), (B-
Powder obtained by coagulation, heat treatment and dehydration of the latex of 3) and the above copolymers (A-1), (A-2) and (A-3)
Are mixed at a ratio corresponding to the amount of rubber shown in Table 1, dewatered and melt-kneaded in an extruder to obtain ABS resin (I-1), (I-
2) and (I-3) pellets were obtained. 2) Production of powdery ABS resin (I-4) The latex of the above graft copolymer (B-4) and the latex of the above copolymer (A-4) were mixed, and 2 parts of calcium chloride was added to coagulate. ABS, heat treatment, dehydration and drying
A resin (I-4) powder was obtained.

[0032]

[Table 1]

2. Production of PVC resin (II) By a suspension polymerization method (Japanese Patent Application No. 9-47267), 0.04 parts of 2-ethylhexyl peroxycarbonate was used as an initiator at a polymerization temperature of 60 ° C., and the internal pressure of the reactor was 7 kg / cm ^2. G
Polymerized until the pressure is reduced to PVC resin (II-1),
(II-2), (II-3) and (II-4) were synthesized. Table 2 shows the composition (parts) and the viscosity average degree of polymerization.

[0034]

[Table 2]

3. Alkyl (meth) acrylate resin (I
Production of II) (1) Production of copolymer (C) Copolymers (C-1), (C-2), (C-3), (C-
4) was synthesized by a known emulsion polymerization method (described in JP-A-4-004245) using a polymerization temperature of 60 ° C., a polymerization time of 8 hours, and potassium persulfate as an initiator.
Table 3 shows the composition (parts) and reduced viscosity. (2) Production of copolymer (D) Copolymers (D-1), (D-2), (D-3), (D-
4) is a known emulsion polymerization method (JP-A-61-233035).
The polymerization temperature was 60 ° C., the polymerization time was 8 hours, and cumene hydroperoxide 0.3 was used as an initiator.
Were synthesized using Composition (parts) and reduced viscosity (dl /
g) is shown in Table 3. (3) Preparation of alkyl (meth) acrylate resin (III) A latex of copolymer (C) and a latex of copolymer (D) are mixed so that the solid content ratio becomes 1/1, and 2 parts of calcium chloride are mixed. And solidified. The coagulated slurry was heat-treated, dehydrated and dried to obtain powders of the alkyl (meth) acrylate resins (III-1), (III-2), (III-3), and (III-4).

[0036]

[Table 3]

4. Production of ABS-PVC alloy compound ABS resin (I), PVC resin (I
I), an alkyl (meth) acrylate-based resin (III), a stabilizer (IV) shown in Table 4, and a lubricant (V) shown in Table 5 in a ratio (parts) shown in Table 6 in a 20 L blender manufactured by Tabata Co., Ltd. (With steam heating jacket). In the blending conditions, stirring was started at room temperature, heating was started at the same time, and the stirring was stopped when 90 ° C. was reached. It took 8 minutes to reach 90 ° C. After stopping, water was passed through the jacket and cooled with stirring to 65 ° C. or lower to obtain a compound for ABS-PVC alloy.

5. Production of ABS-PVC Alloy Pellets A compound for ABS-PVC alloy, in which the components (I) to (V) were blended in the ratio (parts) shown in Table 6, was heated at 190 ° C. with a 40 mm single screw extruder manufactured by Tabata Co., Ltd. The mixture was melt-kneaded at the resin temperature to produce ABS-PVC alloy pellets.

6. Manufacture of ABS-PVC alloy flame-retardant housing The above ABS-PVC alloy pellets were resinized at 205 ° C using an injection molding machine model 850-MG-160 (screw CR = 2.2) manufactured by Mitsubishi Heavy Industries, Ltd. At temperature, 17
An inch display (back type, molded product weight 1.8 kg, wall thickness 2.7 mm, direct gate) was molded.

[0040]

[Table 4]

Stabilizer-1: Dibutyltin maleate polymer Stabilizer-2: Dioctyltinmalate Stabilizer-3: Dibutyltin (3-mercapto) propionate Stabilizer-4: Dibutyltin (2-ethylhexyl ester) malate Stabilizer-5 : Dibutyltin (dibenzyl ester) malate stabilizer-6: dibutyltin (3-mercapto) propionate stabilizer-7: (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (molecular weight 703) stabilizer- 8: n-octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate (molecular weight 530) Stabilizer-9: 4,4'-butylidenebis- (6-t-butyl-3-methylphenol) (molecular weight 342) Stabilizer-10: Calcium stearate stabilizer -11: Epoxidized soybean oil

[0042]

[Table 5]

Lubricant-1: pentaerythritol tetrastearate Lubricant-2: Stearyl stearate Lubricant-3: Glyceride tristearate Lubricant-4: Stearamide Lubricant-5: Ethylene bis (stearic amide) Lubricant-6: Oxidation Polyethylene wax (molecular weight 200
0) Lubricant-7: polyethylene wax (molecular weight 800) Lubricant-8: magnesium stearate Lubricant-9: stearic acid

[0044]

[Table 6]

In Tables 1 to 6, the reduced viscosity, viscosity average degree of polymerization, graft ratio, volume average particle size of the rubber polymer, polymerization conversion, and properties of the ABS-PVC alloy are measured or evaluated by the following methods. did. [Reduced viscosity] 0.3 dl / g in dimethylformamide solution
After dissolving the copolymer (A), the copolymer (C) and the copolymer (D) at a concentration of, the solution viscosity was measured at 30 ° C. using an Ostwald viscometer and calculated. [Viscosity average polymerization degree] The viscosity average molecular weight of the vinyl chloride resin (II) was measured based on JIS K6721. [Graft ratio] The graft ratio is determined by the graft copolymer (B).
Was dissolved in methyl ethyl ketone and centrifuged to obtain a methyl ethyl ketone soluble and insoluble content of the thermoplastic resin composition. Methanol was added to the methyl ethyl ketone soluble matter to cause precipitation, and the precipitate was taken out. The graft ratio was determined from the ratio of the precipitate to the methyl ethyl ketone insoluble component and the polymerization conversion ratio. [Volume average particle diameter of rubber polymer] The rubber polymer latex was measured with a Microtrac UPA particle size analyzer manufactured by Nikkiso Co., Ltd. [Polymerization conversion rate] The polymerization conversion rate was calculated by gas chromatography analysis.

[Characteristics of ABS-PVC alloy] Injection moldability was evaluated by using the above 17 inch display (back type), and using the following five-point evaluation method for resin filling (short, burr), burnt, and silver. Was visually determined. 5 points: good filling, no burns or silver 4 points: good filling properties, little burns and silver 3 points: Good filling properties, and some burns and silver are observed. 2 points: Filling properties are somewhat poor, and burns and silver are slightly observed. 1 point: The filling property is poor, and burns and silver are considerably observed.

The fluidity was determined by FAS1 manufactured by FANUC CORPORATION.
Using a 00B injection molding machine, cylinder temperature 190 ° C,
At an injection pressure of 1350 kg / cm ² , the flow length (unit: mm) of the resin in a spiral mold having a thickness of 3 mm was evaluated.

Heat resistance (HDT) is as per ASTM D648
Of 18.6 kg / cm ² load (unit: ° C.). The test pieces used for the above-mentioned IZOD impact strength and heat resistance were molded at a resin temperature of 205 ° C. using a FAS100B injection molding machine manufactured by FANUC CORPORATION and provided for evaluation.

The impact resistance was evaluated by IZOD impact strength. The IZOD impact strength is based on the ASTM D-256 standard (1
/ 4 inch thickness) at 23 ° C. (unit:
Kgcm / cm).

The flame retardancy was evaluated by a 1/10 inch thick bar according to the UL-94 vertical test method of the United States UL standard.

The appearance was evaluated by using the above-mentioned 17-inch display (back type) and visually determining the uniformity of the surface gloss and the unevenness of the gate portion and the weld portion by the following five-point evaluation method. 5 points: The gloss is uniform, and there is no unevenness in the gate portion and the weld portion. 4 points: The gloss is almost uniform, and the unevenness of the gate portion and the weld portion is hardly noticeable. 3 points: The gloss is almost uniform, but the gate portion and the weld portion have some unevenness. 2 points: gloss is almost uniform, but unevenness in the gate portion and weld portion is conspicuous. 1 point: The unevenness of the gate portion and the weld portion is considerably conspicuous without gloss uniformity.

In Table 6, the larger the numerical value, the better the characteristics. From the results in Table 6, Examples 1 to 6
It is clear that the ABS-PVC alloy of the present invention represented by the formula (1) is particularly excellent in injection moldability, impact resistance, appearance (surface properties), heat resistance, flame retardancy, and fluidity.

[0053]

As described above, the ABS-PVC of the present invention is used.
Alloy compounds are particularly suitable for injection molding, impact resistance,
It has excellent appearance (surface properties), good heat resistance, good flame retardancy and good fluidity, and is useful for OA equipment, office machines, housings for electronic and electrical equipment, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33:06)

Claims (8)

[Claims] 1. The resin composition comprises 20 to 70% by weight of a pellet-like ABS resin (I) and 80 to 30% by weight of a powdery PVC resin (II) as shown below, and based on 100 parts by weight of the PVC resin (II). And 0.5 to 20 parts by weight of an alkyl (meth) acrylate resin (III) and a stabilizer (IV) 3
A compound for ABS-PVC alloy, comprising from about 12 parts by weight to 3 parts by weight of a lubricant (V). (I) ABS resin in pellet form: 15 to 35% by weight of a vinyl cyanide compound, 85 to 65% by weight of an aromatic vinyl compound, and 0 to 20% by weight of another copolymerizable vinyl compound (100% by weight in total) Copolymer (A) 40-85 having a reduced viscosity of 0.20 to 0.55 dl / g, polymerized by a polymerization method.
15 to 35% by weight of a vinyl cyanide compound, 85 to 65% by weight of an aromatic vinyl compound, and 0 to 20% by weight of another copolymerizable vinyl compound with respect to 40% to 85% by weight of a diene rubber (R). % (Total 100% by weight) of a graft copolymer (B) obtained by emulsion polymerization of 60 to 15% by weight of a monomer mixture (M) of 60 to 15% by weight, and a rubber content of 10 to 40%. ABS resin pellets in weight%. (II) PVC resin: viscosity average degree of polymerization of 400 to 800,
A vinyl chloride polymer or copolymer containing 80% by weight or more of vinyl chloride. (III) Alkyl (meth) acrylate resin: 40 to 100% by weight of acrylic (meth) acrylate, 60 to 0% by weight of another copolymerizable monomer, and a reduced viscosity of 1.5
10 to 10 dl / g of the copolymer (C) and 20 to 100% by weight of the alkyl (meth) acrylate, 80 to 0% by weight of another copolymerizable monomer, and a reduced viscosity of 0.05 to 0.
At least one resin selected from the group consisting of 5 dl / g copolymer (D); (IV) Stabilizer: a stabilizer comprising 55 to 100% by weight of a tin stabilizer and 45 to 0% by weight of another stabilizer. (V) Lubricant: at least one lubricant selected from the group consisting of ester lubricants having 10 to 70 carbon atoms, amide lubricants having 10 to 70 carbon atoms, hydrocarbon lubricants, metal soap lubricants and fatty acid lubricants. 2. An ABS resin (I) 2 in the form of a pellet as described below.
5 to 65% by weight and powdery PVC resin (II) 75
-35% by weight, and the PVC resin (II) 100
The alkyl (meth) acrylate resin (I
2. A according to claim 1, comprising II) 1 to 15 parts by weight, stabilizer (IV) 4 to 10 parts by weight, and lubricant (V) 5 to 11 parts by weight.
Compound for BS-PVC alloy. (I) ABS resin in pellet form: acrylonitrile 20
-35% by weight, styrene and / or α-methylstyrene 80-65% by weight, butyl (meth) acrylate and / or
Or 0 to 10% by weight of methyl (meth) acrylate (total 1)
00% by weight) by a bulk polymerization method, having a reduced viscosity of 0.2
5 to 0.50 dl / g of the copolymer (A) 50 to 80% by weight and polybutadiene and / or styrene-butadiene rubber (R) 40 to 80% by weight, acrylonitrile 20 to 33% by weight, styrene 80 to 80% by weight. 67 to 20% by weight of a monomer mixture (M) composed of 67% by weight, 0 to 10% by weight of butyl (meth) acrylate and / or methyl (meth) acrylate (total 100% by weight) was graft-polymerized by an emulsion polymerization method. Graft copolymer (B) 50 to 20% by weight
A pellet-shaped ABS resin having a rubber content of 13 to 35% by weight. (II) PVC resin: viscosity average degree of polymerization of 450 to 700,
A vinyl chloride polymer or copolymer containing 90% by weight or more of vinyl chloride. (III) Alkyl (meth) acrylate resin: 1 to 1 carbon atoms
(Meth) acrylate having 12 alkyl groups 50 to
95% by weight, styrene and / or α-methylstyrene 5
0 to 5% by weight, a copolymer (C) having a reduced viscosity of 1.8 to 9 dl / g, and an alkyl (meth) acrylate of 25 to 25% by weight.
100% by weight, 75 to 0% by weight of styrene and / or α-methylstyrene and / or acrylonitrile,
At least one resin selected from the group consisting of copolymers (D) having a reduced viscosity of 0.1 to 0.45 dl / g. (IV) Stabilizer: 65 to 100% by weight of tin stabilizer and selected from the group consisting of hindered phenolic antioxidants, fatty acid metal salts, epoxy stabilizers, phosphorus stabilizers, and oxides of alkyl earth metals. At least one 35 to 0% by weight
Stabilizer. (V) a lubricant: at least one selected from the group consisting of an ester lubricant having 10 to 70 carbon atoms, an amide lubricant having 10 to 70 carbon atoms, a hydrocarbon lubricant, a metal soap lubricant and a fatty acid lubricant, A lubricant comprising 30% by weight or more of an ester lubricant having 10 to 70 carbon atoms and / or an amide lubricant having 10 to 70 carbon atoms. 3. An expanded rubber having a polybutadiene rubber and / or styrene-butadiene rubber (R) having a particle diameter (volume average particle diameter, the same applies hereinafter) of 100 nm or more in the ABS resin (I) in the form of a pellet is 10% by weight or more. 3. The compound for ABS-PVC alloy according to claim 1, wherein the compound contains polybutadiene rubber and / or styrene-butadiene rubber. 4. An enlarged rubber having a particle size of 150 to 1000 nm, wherein the polybutadiene rubber and / or the styrene-butadiene rubber (R) in the ABS resin (I) in the form of pellets has a particle size of 150 to 1000 nm.
Unexpanded rubber 90-1 with weight% and particle size less than 40-150nm
The ABS-PVC alloy compound according to any one of claims 1 to 3, comprising 0% by weight. 5. A stabilizer (IV) comprising 20 to 80% by weight of a malate tin stabilizer, 5 to 80% by weight of a sulfur tin stabilizer, and 3 to 3 parts of a phenolic antioxidant having a molecular weight of 300 or more.
The compound for ABS-PVC alloy according to any one of claims 1 to 4, which is 40% by weight (total 100% by weight). 6. The composition according to claim 1, wherein the liquid stabilizer in the ABS-PVC alloy compound is 10 to 90% by weight in 100% by weight of the tin stabilizer, and the tin content in the compound is 0.2 to 2% by weight. The compound for ABS-PVC alloy according to any one of claims 1 to 5. 7. A according to any one of claims 1 to 6,
ABS-PVC alloy pellets for injection molding excellent in processability, obtained by melt-kneading a compound for BS-PVC alloy. 8. An OA device, an office machine, and the like having excellent surface properties, obtained by injection molding the ABS-PVC alloy according to claim 1.
Flame-retardant housing for electronic and electrical equipment.