TW201917164A - Chlorine-containing resin composition - Google Patents

Abstract

The present invention provides a chlorine-containing resin composition which uses a Ca-Zn-based stabilizer and sufficiently suppresses blurring or wrinkles on the surface of the molded article even when a continuous production is continued for a long period of time. The present invention relates to a chlorine-containing resin composition comprising (a) a chlorine-containing resin, (b) an organic acid zinc, (c) an oxidized polyethylene wax, (d) hydrotalcite, and (e) β-di ketone compound and / or β- diketone metal salt, and the (c) 1720 cm polyethylene oxide in the FT-IR measurement of wax ^- absorbance ratio of the peak ¹ (1720 cm ^{- - 1} and the peak of 2930 cm ¹ Peak absorbance / 2930 cm ^{- 1} peak absorbance) is 0.05 or more.

Description

Chlorine-containing resin composition

The present invention relates to a chlorine-containing resin composition. More specifically, it relates to a chlorine-containing resin composition which can be preferably used as a material for pipes, joints, building materials, automobile parts and the like.

Chlorine-containing resins, which are represented by polyvinyl chloride, have high flexibility, are easy to process, and have physical properties such as flame retardancy. Therefore, they are used in agricultural films, wires, pipes, and resin window frames. Various compositions having characteristics according to the requirements are proposed (see Patent Documents 1 to 4). In general, the vinyl chloride resin composition is insufficient in thermal stability, and a stabilizer is used in order to impart thermal stability during processing. Pb-based stabilizers or Sn-based stabilizers have been widely used in the past, however, in recent years, the use of Ca-Zn-based stabilizers having lower toxicity, that is, without Pb, has been increasing for environmental considerations. [Prior Technical Literature] [Patent Literature]

Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

[Problems to be solved by the invention]

When a molded article of a chlorine-containing resin composition is produced by using "an increased Ca-Zn stabilizer in recent years", if it is subjected to continuous production for a long period of time, there is a problem such as blurring or wrinkling on the surface of the molded article. , and significantly reduce the problem of productivity. The Sn-based stabilizer is mainly a liquid stabilizer, or a low-melting-point compound having a resin softening temperature or lower even if it is a solid. On the other hand, the Ca-Zn-based stabilizer contains a large amount of "inorganic substances such as hydrotalcite having no melting point", and Since the solubility or compatibility of the chlorine resin is completely different, if it is used in a Sn-based stabilizer to improve the defects of the molded article, the problem cannot be solved, and it is necessary to develop a solution corresponding to the Ca-Zn-based stabilizer. The method of the subject.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a chlorine-containing resin composition which uses a Ca-Zn-based stabilizer and which is sufficiently suppressed even in the case of continuous production over a long period of time. The surface of the molded article is blurred or wrinkled. [Technical means to solve the problem]

The present inventors conducted various studies on a method for suppressing blurring or wrinkling of a chlorine-containing resin composition using a Ca-Zn-based stabilizer, and as a result, it was found that a chlorine-containing resin composition containing an organic acid zinc as a stabilizer was used. Further, in order to further contain a specific oxidized polyethylene wax, hydrotalcite, and a β-diketone compound and/or a β-diketone metal salt, it can be sufficiently suppressed even in the case of continuous production for a long period of time. The surface of the molded article is blurred or wrinkled, thereby completing the present invention.

That is, the present invention is a chlorine-containing resin composition containing (a) a chlorine-containing resin, (b) an organic acid zinc, (c) an oxidized polyethylene wax, (d) hydrotalcite, and (e) β- diketone compound and / or β- diketone metal salt, and the (c) oxidized polyethylene wax in the FT-IR (fourier transform infrared radiation , Fourier transform infrared spectroscopy) measurement of 1720 cm ^- peak of 2930 cm ^{1-- a} ratio of the peak absorbance (1720 cm ^{- 1} peak absorbance / 2930 cm ^{- 1} peak absorbance) is 0.05 or more.

The above (c) oxidized polyethylene wax preferably has an acid value of 1 mgKOH/g or more.

The above (c) oxidized polyethylene wax preferably has a density of 0.95 g/cm ³ or less.

The above (c) oxidized polyethylene wax preferably has a melting point of 80 ° C or higher.

The above (c) oxidized polyethylene wax preferably has a melt viscosity at 140 ° C of 1000 cps or less.

The above (d) hydrotalcite preferably has an oil absorption of 50 ml/100 g or less.

The chlorine-containing resin composition preferably further contains (f) dipentaerythritol hexastearate.

The chlorine-containing resin composition is preferably 5% by weight or less based on the total amount of the plasticizer of the composition.

The chlorine-containing resin composition is preferably further contained in an amount of 30 parts by mass or less based on 100 parts by mass of the chlorine-containing resin. [Effects of the Invention]

The chlorine-containing resin composition of the present invention not only uses a stabilizer which is low in toxicity in consideration of the environment, but also sufficiently suppresses blurring or wrinkling of the surface of the molded article even in the case where continuous production is carried out for a long period of time. Therefore, it can be preferably used as a material for various molded articles such as pipe pipes, joints, building materials, and automobile parts.

In the following, an example of the present invention will be specifically described. However, the present invention is not limited to the following description, and may be appropriately modified and applied without departing from the spirit and scope of the invention.

<Chlorine-Containing Resin Composition> The chlorine-containing resin composition of the present invention contains (a) a chlorine-containing resin, (b) an organic acid zinc, (c) an oxidized polyethylene wax, (d) a hydrotalcite, and (e) a β-diketone compound and/or a β-diketone metal salt. These components may be contained alone or in combination of two or more. In addition, components other than these may also be contained. Hereinafter, each component of (a) to (e) will be described in order.

[Chlorine-containing resin] The chlorine-containing resin is not particularly limited as long as it is a resin (polymer) containing a chlorine atom, and is preferably a vinyl chloride resin. Thereby, a molded body excellent in flexibility or flame retardancy can be obtained.

Examples of the vinyl chloride-based resin include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymer, and vinyl chloride-ethylene-acetic acid. Vinyl ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-amine copolymer , vinyl chloride-acrylate copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isopentane Ene copolymer, vinyl chloride-chloropropene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride - a copolymer such as an acrylonitrile copolymer or a vinyl chloride-methyleneimine copolymer. Further, a blend of a chlorine-containing resin and a chlorine-free resin may be used, and a polymerization method for obtaining a vinyl chloride resin is not particularly limited.

[Organic Acid Zinc] The chlorine-containing resin composition of the present invention stabilizes the chlorine of the chlorine-containing resin by containing the organic acid zinc, thereby suppressing discoloration during processing or at the time of use. The organic acid zinc is a less toxic stabilizer that does not contain Pb. Further, such a Pb-free stabilizer and not classified as a Sn-based stabilizer are generally referred to as a Ca-Zn-based stabilizer. The Ca-Zn stabilizer not only means a stabilizer containing both of Ca and Zn, but also a stabilizer containing only Zn, or a stabilizer containing no both Ca and Zn and also containing no Sn. In addition, the Ca-Zn-based stabilizer also includes a stabilizer containing a metal element other than Pb such as Sn in addition to Ca and Zn. In the present invention, when the content is 0.5 parts by mass or less based on 100 parts by mass of the chlorine-containing resin when it is added to the chlorine-containing resin, the stabilizer is classified into a Ca-Zn system. The stabilizer is classified into a Sn-based stabilizer when the content of Sn is more than 0.5 parts by mass.

The organic acid in the organic acid zinc is not particularly limited, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, and neodecanoic acid. , citric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzene Formic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzene Formic acid, acrylic acid, n-propyl benzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, ethoxylated benzoic acid, salicylic acid, p-third octyl salicylic acid, anti-oil Monobasic organic carboxylic acid such as acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chloro-phthalic acid Dibasic organic carboxylic acids such as acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, etc.; : monoester or monodecylamine compound of dicarboxylic organic carboxylic acid, butane tricarboxylic acid, butane tetracarboxylic acid, hemilimic acid, 1,2,4-benzenetricarboxylic acid, 1,2, a di- or tri-ester of a ternary or quaternary organic carboxylic acid such as 3,5-benzenetetracarboxylic acid or pyroic acid. Among them, preferred are higher fatty acids having 12 to 20 carbon atoms. Specifically, it is preferably a zinc salt of myristic acid, palmitic acid, isostearic acid or stearic acid which has appropriate lubricity and compatibility with a chlorine-containing resin.

The content of the organic acid zinc is not particularly limited, and is preferably 0.01 parts by mass or more based on 100 parts by mass of the chlorine-containing resin. Thereby, discoloration can be suppressed. More preferably, it is 0.1 mass part or more. In addition, it is preferably 5 parts by mass or less, whereby the heat resistance can be further improved, and the appearance of the molded body is not further deteriorated, and the color tone is further improved. More preferably, it is 2 mass parts or less.

[Oxidized polyethylene wax] The chlorine-containing resin composition of the present invention comprising an oxidized polyethylene wax in 1720 cm of the oxidized polyethylene wax measured in FT-IR ^- absorbance ratio of the peak of ^{1 -} Peak ¹ and the 2930 cm (1720 cm ^{- 1} peak absorbance / 2930 cm ^{- 1} peak absorbance) is 0.05 or more. 1720 cm ^{- 1} peak value based upon the peak for oxidized polyethylene wax, 2930 cm ^{- 1} peak peak represents a hydrocarbon-based bond of polyethylene wax. By using a polyethylene wax having a ratio of the peaks of 0.05 or more, that is, oxidized to a certain extent or more, as an oxidized polyethylene wax, the effect of reducing the surface defects of the molded article can be exhibited.

The oxidized polyethylene wax preferably has an acid value of 1 mgKOH/g or more. When the acid value is 1 mgKOH/g or more, the compatibility with the resin is more sufficiently enhanced, and the effect of suppressing the appearance of the molded article is suppressed. The acid value of the oxidized polyethylene wax is more preferably 5 mgKOH/g or more, and still more preferably 10 mgKOH/g or more. Further, it is preferably 30 mgKOH/g or less.

The oxidized polyethylene wax preferably has a density of 1.00 g/cm ³ or less. When the density is 1.00 g/cm ³ or less, the melt viscosity of the resin is lowered, and the formability is further improved. The density of the oxidized polyethylene wax is more preferably 0.95 g/cm ³ or less.

The oxidized polyethylene wax preferably has a melting point of 80 ° C or higher. When the melting point is 80° C. or higher, the sublimate or the like is reduced, and the chlorine-containing resin composition of the present invention exhibits an effect of reducing surface defects of the molded article in terms of moldability. The melting point of the oxidized polyethylene wax is more preferably 85 ° C or higher, and still more preferably 90 ° C or higher. Further, the melting point of the oxidized polyethylene wax is usually 150 ° C or lower.

The oxidized polyethylene wax preferably has a viscosity at 140 ° C of 1000 cps or less. When the viscosity at 140 ° C is 1000 cps or less, the chlorine-containing resin composition of the present invention is excellent in moldability. The viscosity of the oxidized polyethylene wax at 140 ° C is preferably 800 cps or less. More preferably 500 cps or less.

In the present specification, the acid value, density, melting point of the oxidized polyethylene wax and the viscosity at 140 ° C were all measured according to the methods described in the examples.

Examples of the oxidized polyethylene wax include the Hi-Wax series manufactured by Mitsui Chemicals Co., Ltd., the SANWAX series manufactured by Sanyo Chemical Industries Co., Ltd., the Viscol series manufactured by Sanyo Chemical Industries Co., Ltd., the Luvax series manufactured by Nippon Seiko Co., Ltd., and Honeywell Co., Ltd. In the AC series or the like, those satisfying the above physical properties can be suitably used.

The content of the oxidized polyethylene wax in the chlorine-containing resin composition of the present invention is preferably 0.01 to 2.0 parts by mass based on 100 parts by mass of the chlorine-containing resin. Thereby, the effect of suppressing the appearance defect of a molded article is fully exhibited. More preferably, it is 0.01 to 1.5 parts by mass, and further preferably 0.01 to 1.0 part by mass.

[Hydrohydrate] The hydrotalcite contained in the chlorine-containing resin composition of the present invention is not particularly limited, and preferably contains magnesium (Mg) and/or zinc (Zn) and aluminum (Al).

As the above hydrotalcite-type powder, it is particularly preferable to use the following general formula (1): {(Mg) _x (Zn) _y } (Al) _z (OH) ₂ (A ^{n -} ) _{x / n} · mH ₂ O ( 1) (wherein, A ^{n -} represents an interlayer anion of n valence. x, y, and z are numbers satisfying 0 < x < 1, 0 ≦ y < 1, 0.2 ≦ z ≦ 0.4, x + y + z = 1 And the ratio of x + y to z {(x + y) / z} is 2.2 or less. n and m are respectively represented by numbers satisfying 1 ≦ n ≦ 4 and 0 ≦ m). Thereby, the heat resistance or thermal stability of the chlorine-containing resin composition is further improved.

In the above formula (1), the n-valent interlayer anion is not particularly limited, and from the viewpoint of reduction in reactivity and environmental load, it is preferably selected from hydroxide ions (OH ^- ) and carbonate ions ( At least one of the group consisting of CO ₃ ^{2 -} ) and sulfate ion (SO ₄ ^{2 -} ). Among them, carbonate ions are preferred.

x, y, and z are numbers satisfying 0<x<1, 0≦y<1, 0.2≦z≦0.4, x+y+z=1, and the ratio of x+y to z{(x+y)/ z} is 2.2 or less. Here, the one with y = 0 is called Mg/Al hydrotalcite, and the one with 0 < y is called zinc modified hydrotalcite. In the present invention, any of these may preferably be used.

The ratio of x + y to z {(x + y) / z} is preferably 2.1 or less, more preferably 2.05 or less. The lower limit is not particularly limited, but is preferably 1.9 or more, and more preferably 2.0 or more.

n is a number satisfying 1≦n≦4, and may be appropriately adjusted according to the valence of the interlayer anion.

The hydrotalcite preferably has an oil absorption of 50 ml/100 g or less. Thereby, the gloss of the molded article obtained from the chlorine-containing resin composition of the present invention is improved. The oil absorbing amount of the hydrotalcite is more preferably 45 ml/100 g or less, and further preferably 40 ml/100 g or less. Further, from the viewpoint of heat resistance, it is preferably 5 ml/100 g or more. More preferably 10 ml/100 g or more.

In the present specification, the oil absorption amount of the hydrotalcite-type powder is measured in accordance with JIS K5101-13-1 (2004: refined linseed oil method).

The shape of the particles of the hydrotalcite is not particularly limited, and examples thereof include a plate shape, a spherical shape, and a disk shape. Among them, a plate or a disk is preferable. Further, the particle shape can be observed by a scanning electron microscope or the like.

The average particle diameter of the hydrotalcite particles is, for example, preferably 0.1 μm or more and 2.0 μm or less. Thereby, the dispersibility in the chlorine-containing resin is improved, and the effects of the present invention are further improved. More preferably, it is 0.3 μm or more, and more preferably 1.5 μm or less.

In the present specification, the average particle diameter can be measured, for example, in the form of D50 using a laser diffraction particle size distribution measuring apparatus (LA950 manufactured by HORIBA). By D50 is meant the 50% cumulative particle size under the volume basis.

The specific surface area (also referred to as SSA) of the above hydrotalcite is, for example, preferably 1 m ² /g or more and 50 m ² /g or less. Thereby, the dispersibility in the chlorine-containing resin is improved, and the effects of the present invention are further improved. It is more preferably 5 m ² /g or more, further preferably 10 m ² /g or more, more preferably 40 m ² /g or less, still more preferably 30 m ² /g or less. When the specific surface area is in this range, a resin composition excellent in heat resistance can be obtained.

In the present specification, the specific surface area means a BET specific surface area (also referred to as SSA) obtained by the BET method. The BET method is a gas adsorption method in which gas particles such as nitrogen are adsorbed to solid particles, and a specific surface area is measured based on the amount of adsorption, and the single molecule adsorption amount VM is determined by the BET equation based on the relationship between the pressure P and the adsorption amount V. Specific surface area. Specifically, the BET specific surface area was measured by the following conditions.

[Measurement conditions of specific surface area] Machine: manufactured by Mountech, Macsorb Model HM-1220 Adsorbed gas: Nitrogen (N ₂ ) Degassing conditions of external degassing apparatus: Degassing conditions of the apparatus of the apparatus of 105 ° C - 15 minutes specific surface area :105°C-5 minutes

The particles in the powder of the hydrotalcite may also have a coating layer. In this case, it is preferred that the hydrotalcite containing the particles having the coating layer satisfy the physical properties (particle shape, average particle diameter, specific surface area, and the like). The coating layer is not particularly limited, and it is preferably a surface treated with a surface treatment agent to be coated.

The surface treatment agent is not particularly limited, and examples thereof include a coupling agent such as a higher fatty acid, a higher fatty acid metal salt (metal soap), an anionic surfactant, a phosphate ester, a decane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Further, one type or two or more types may be used.

Specific examples of the surface treatment agent include higher fatty acids such as stearic acid, oleic acid, sinapic acid, palmitic acid, and lauric acid, and metal salts such as lithium salts, sodium salts, and potassium salts of the higher fatty acids; and stearin; a sulfate ester of a higher alcohol such as an alcohol or an oleyl alcohol; a sulfate salt of a polyethylene glycol ether; a guanamine bond sulfate salt; an ether bond sulfonate; an ester bond sulfonate; a guanamine bond alkyl aryl sulfonic acid; An anionic surfactant such as a salt or an ether bond alkylarylsulfonate; a mono- or di-ester of orthophosphoric acid with oleyl alcohol, stearyl alcohol or the like, or a mixture thereof, or an acid or alkali metal salt or amine thereof Phosphate such as salt; vinyl ethoxy decane, γ-methyl propylene methoxy propyl trimethyl decane, vinyl tris(2-methoxyethoxy) decane, γ-aminopropyl trimethoxy a decane coupling agent such as decane or the like; isopropyl triisostearyl isopropyl titanate, isopropyl tris(dioctyl pyrophosphonium oxy) titanate, isopropyl tris-phenylbenzenesulfonyl titanate, etc. A coupling agent; an alkali coupling agent such as acetoxy aluminum diisopropyl ester.

The amount of the surface treatment agent to be used is not particularly limited. For example, it is preferably 100% by mass of the hydrotalcite containing the particles having the coating layer, and the coating amount obtained by the surface treatment agent is 0.1 to 30 mass. The range of % is used to adjust the amount of surface treatment agent used. More preferably, it is in the range of 0.1 to 20% by mass.

In the resin composition, the content of the hydrotalcite is preferably 0.05 parts by mass or more, and preferably 10 parts by mass or less, based on 100 parts by mass of the chlorine-containing resin. Thereby, heat resistance and thermal stability are further improved. It is more preferably 0.1 part by mass or more, still more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less.

[β-diketone compound, β-diketone metal salt] Further, the chlorine-containing resin composition of the present invention can form coloring property during molding by containing a β-diketone compound and/or a β-diketone metal salt. improve.

The β-diketone compound is not particularly limited, and is preferably, for example, ethyl acetonide or stearyl decyl methane, benzylidene ethane methyl, benzoylmethane or stearyl sulfhydryl. Benzylmethane, octyl benzhydryl methane, bis(4-octyl benzhydryl)methane, 4-methoxybenzimidylbenzylidene methane, bis(4-carboxymethylbenzene Mercapto) methane, 2-carboxymethylbenzimidyloctyloctylmethane, 2-benzylidenecyclohexane or the like, alkylmercaptoarylmethane or diarylmethylmethane. As the β-diketone metal salt, a metal salt of the above β-diketone compound is preferred. The metal type of the metal salt is not particularly limited, and examples thereof include calcium or zinc.

The content of the β-diketone compound and/or the β-diketone metal salt in the resin composition is preferably 2.0 parts by mass or less based on 100 parts by mass of the chlorine-containing resin. More preferably, it is 0.01 to 1.0 part by mass.

[Release Agent] Further, the chlorine-containing resin composition of the present invention preferably contains a release agent. Examples of the release agent include dipentaerythritol hexastearate, pentaerythritol tetrastearate, and the like, and among them, dipentaerythritol hexastearate is preferably contained. Thereby, blurring or wrinkling of the chlorine-containing resin composition of the present invention can be more sufficiently suppressed.

In the case where the chlorine-containing resin composition of the present invention contains a release agent, the content thereof is not particularly limited, and is, for example, preferably 0.01 to 5.0 parts by mass based on 100 parts by mass of the chlorine-containing resin. More preferably, it is 0.01 to 2.0 parts by mass.

[Filler] Further, the chlorine-containing resin composition of the present invention preferably contains a filler. As a result, the dimensional stability of the molded article or the strength of the molded article is improved, so that it is a resin composition which is preferably used for a molded article. The filler also functions as a neutralizing agent.

The filler is not particularly limited, and examples thereof include inorganic powders, inorganic oxides, inorganic hydroxides, and the like, and examples thereof include zinc, titanium, iron, lanthanum, cerium, calcium, lanthanum, aluminum, and magnesium. Salts, oxides, hydroxides, and composite oxides of cerium, boron, and zirconium. The salt is not particularly limited, and examples thereof include a sulfate, a carbonate, a chloride salt, an acetate, and a nitrate. Specific examples thereof include calcium carbonate, zinc carbonate, magnesium carbonate, cerium oxide, zinc oxide, titanium oxide, cerium oxide, iron oxide, barium sulfate, barium sulfate, magnesium sulfate, cerium oxide, aluminum oxide, magnesium oxide, and cerium. Zinc acid, zinc titanate, barium titanate, talc, etc., among which calcium carbonate is preferred.

Among the calcium carbonates, those having a specific surface area (BET specific surface area) of less than 25 m ² /g are preferred. More preferably, it is 23 m ² /g or less, further preferably 20 m ² /g or less, particularly preferably 18 m ² /g or less, and the lower limit is preferably 0.1 m ² /g or more. More preferably, it is 0.5 m ² /g or more. When it exceeds the above range, there is a problem that an adverse effect such as precipitation occurs during processing.

In the case where the resin composition contains a filler, the content thereof is not particularly limited. For example, it is preferably 40 parts by mass or less based on 100 parts by mass of the chlorine-containing resin. When it exceeds 40 mass parts, precipitation may not be suppressed. It is more preferably 30 parts by mass or less, still more preferably 1 to 30 parts by mass. Furthermore, it is more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and the lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 parts by mass. More than the mass. The content of calcium carbonate which is preferably a specific surface area of 20 m ² /g or less is in the above preferred range.

[Other Components] The chlorine-containing resin composition of the present invention may further contain other components as needed. For example, various additives such as a heat-resistant auxiliary agent, a lubricant other than the oxidized polyethylene wax of the above (c), an ultraviolet absorber, an antioxidant, a crosslinking assistant, and a plasticizer may be mentioned. The various additives are not particularly limited, and examples of the heat-resistant auxiliary include a polyol compound such as diheptaerythritol or an epoxy compound such as an epoxy resin; and examples of the lubricant include stearic acid monoglyceride and palmitic acid a glycerol ester, stearic acid, palmitic acid, or a polyethylene wax other than the oxidized polyethylene wax of the above (c); examples of the ultraviolet absorber include a benzophenone compound, a benzotriazole compound, and an aromatic benzene. Examples of the acid ester compound include a phenol compound; examples of the crosslinking aid include trimethylolpropane trimethacrylate and dipentaerythritol hexaacrylate; and plasticizing; The agent may, for example, be dioctyl phthalate (DOP) or trioctyl trimellitate (TOTM), dioctyl adipate (DOA) or the like.

The chlorine-containing resin composition of the present invention is preferably 5% by weight or less based on the total amount of the plasticizer of the composition. In the case of a molded article obtained from a hard resin composition having a small content of a plasticizer, appearance defects are likely to occur. Therefore, in the case where the resin composition is a hardener having a small content of the plasticizer, the effects of the present invention are more apparent. The content of the plasticizer is more preferably 1.0% by weight or less, still more preferably 0.01% by weight or less. [Examples]

In order to explain the present invention in detail, the embodiments are enumerated below, but the invention is not limited to the embodiments.

1. Raw materials The raw materials described in Table 1-1 and Table 1-2 below are as follows. (a) Chlorine-containing resin Vinyl chloride resin: manufactured by Shin-Etsu Chemical Co., Ltd., TK-1000, polymerization degree 1000

(b) Zinc organic acid Zinc stearate: manufactured by 堺Chemical Industries, Inc., SZ-P (Ca-Zn stabilizer)

(c) Oxidized polyethylene wax AC polyethylene 629A: manufactured by Honeywell AC polyethylene 656: manufactured by Honeywell AC polyethylene 307A: manufactured by Honeywell AC polyethylene 316A: manufactured by Honeywell AC polyethylene 6A: manufactured by Honeywell

(d) Hydrotalcite The manufacturing process of the hydrotalcite described in Example 4 of Japanese Patent No. 5560014 discloses various changes in the molar ratios of magnesium sulfate, aluminum sulfate, and zinc sulfate, and manufacturing conditions to synthesize The hydrotalcite-type powder described in Table 1-1 and Table 1-2 was selected by measuring the oil absorption amount and the specific surface area by the following method each time.

(e) β-diketone compound, β-diketone metal salt, benzoylmethane methane: manufactured by RHODIA, Rhodiastab 83P

(f) Filler calcium carbonate: KS-1000 manufactured by CALFINE Co., Ltd., specific surface area 1.15 m ² /g

(g) Other components calcium stearate: manufactured by 堺Chemical Industries, Inc., SC-P (Ca-Zn stabilizer) Dipentaerythritol: manufactured by Kwong Wing Chemical Co., Ltd., Dipentarit 300 Polyethylene wax: manufactured by Mitsui Chemicals, Hi-Wax 220MP Ester Wax (D-Pentaerythritol Hestearate): Riken Vitamin, Rikester SL-02

Examples 1 to 8 and Comparative Examples 1 to 7 The physical properties of the oxidized polyethylene wax and the hydrotalcite used in the examples and the comparative examples, and the resin composition prepared by using the oxidized polyethylene wax or hydrotalcite thereof. The composition of each component is shown in Table 1-1 and Table 1-2. The physical properties of the oxidized polyethylene wax and the hydrotalcite are measured by the following measurement methods. Further, in Table 1-1 and Table 1-2, the obtained resin composition also showed the evaluation results of the wrinkles or glossiness of the surface of the molded article evaluated by the following method.

<Measurement of physical properties of oxidized polyethylene wax> [Acid value] Measured in accordance with ASTM D-1386. [Density] Measured in accordance with ASTM D-1505. [Melting point (drop point)] Measured in accordance with ASTM D-3954. [Viscosity at 140 ° C] The viscosity at 140 ° C was measured by a Brookfield viscometer (manufactured by Brookfield). [FT-IR peak intensity ratio] The measurement was carried out by Fourier transform infrared spectroscopy using the following apparatus and measurement method. Manufacturer Name: Thermo Fisher Scientific Model: NICOLET 4700 Determination method: ATR method (attenuated total reflectance method) / 1 reflection (using flat plate: diamond 稜鏡 plate) Measurement order: (1) Not mounted on the plate The background value is determined for any item. (2) After measuring the background value, a sample of about 1 tablespoon was pressed against the plate to measure. (3) After measuring the sample, perform "Advanced ATR Correction" and use this as the measurement result. <Measurement of physical properties of hydrotalcite> [Oil absorption amount] Measured according to JIS K5101-13-1 (2004: refined linseed oil method).

<Forming process> The above-mentioned LABO extruder (conical type 2D20C type manufactured by Toyo Seiki Co., Ltd.) having a suction setting machine having a cooling function (a device for smoothing the surface properties of a molded article) is used. The resin composition was extruded into a pipe tube for 5 hours, and cut at regular intervals to obtain a pipe tube molded article. The extrusion conditions were set as follows. The temperature of the cylinder is from the position close to the raw material input port, and the temperature is 1:175 °C, the temperature of the cylinder is 2:180 °C, the temperature of the cylinder is 3:185 °C, and the temperature of the adapter mold is set to 185 °C. The mold 1 was set to 180 ° C, and the mold 2 was set to 205 ° C. The mold uses a mold for the pipe.

<Evaluation of Resin Composition> [Wrinkle] The wrinkle generation condition of the pipe tube molded article obtained after a certain period of time from the start of the extrusion molding (that is, the occurrence of the flaw of the pipe tube molded article) was visually confirmed, and It is evaluated based on the following criteria. ◎: No scratches were observed in the pipe tube molded article formed after 5 hours. ○: A flaw was confirmed in the pipe tube molded article formed after 3 hours. Δ: A flaw was confirmed in the formed pipe tube molded article after 1 hour. Í: A flaw was confirmed in the pipe tube molded article formed within one hour. [Glossiness] The glossiness of the pipe-tube molded article obtained after a certain period of time from the start of extrusion molding was visually confirmed, and evaluated based on the following criteria. ◎: It was confirmed that the formed pipe tube molded product after 5 hours was kept glossy. ○: Gloss was confirmed after 3 hours, but it was confirmed that the formed pipe tube molded product was dull after 5 hours, and the surface of the formed pipe tube was in a state of being blurred. Δ: Gloss was confirmed after 1 hour, but it was confirmed that the formed pipe tube molded article was dull after 3 hours, and the surface of the formed pipe tube was in a state of being blurred. Í: It is confirmed that it is dull after being formed, and the surface of the formed pipe tube is in a state of being blurred.

[Table 1-1] [Table 1-2]

Table 1-1 and Table 1-2 of the result, it was confirmed by FT-IR measurement contained in the 1720 cm ^{- 1} peak values and 2930 cm ^- absorbance ratio of the peak ¹ of 0.05 or more oxidized polyethylene wax, The occurrence of defects in the surface of the molded article of the chlorine-containing resin composition using the Ca-Zn-based stabilizer can be effectively suppressed.

no

no

Claims (9)

A chlorine-containing resin composition comprising (a) a chlorine-containing resin, (b) an organic acid zinc, (c) an oxidized polyethylene wax, (d) a hydrotalcite, and (e) a β-diketone compound and/or or β- diketone metal salt, and the (c) 1720 cm polyethylene oxide in the FT-IR measurement of wax ^- absorbance ratio of the peak ¹ (1720 cm ^{- - 1} and the peak of the absorbance at 2930 cm & lt peak ^1/2930 The cm ^{- 1} peak absorbance is 0.05 or more. The chlorine-containing resin composition according to claim 1, wherein the (c) oxidized polyethylene wax has an acid value of 1 mgKOH/g or more. The chlorine-containing resin composition according to claim 1 or 2, wherein the (c) oxidized polyethylene wax has a density of 0.95 g/cm ³ or less. The chlorine-containing resin composition according to any one of claims 1 to 3, wherein the (c) oxidized polyethylene wax has a melting point of 80 ° C or higher. The chlorine-containing resin composition according to any one of claims 1 to 4, wherein the (c) oxidized polyethylene wax has a melt viscosity at 140 ° C of 1000 cps or less. The chlorine-containing resin composition according to any one of claims 1 to 5, wherein the (d) hydrotalcite has an oil absorption amount of 50 ml/100 g or less. The chlorine-containing resin composition according to any one of claims 1 to 6, wherein the chlorine-containing resin composition further contains (f) dipentaerythritol hexastearate. The chlorine-containing resin composition according to any one of claims 1 to 7, wherein the content of the plasticizer relative to the entire composition is 5% by weight or less. The chlorine-containing resin composition according to any one of claims 1 to 8, which further contains 30 parts by mass or less of calcium carbonate based on 100 parts by mass of the chlorine-containing resin.