TWI772477B - Chlorine-containing resin composition - Google Patents

Abstract

The present invention provides a chlorine-containing resin composition using a Ca-Zn-based stabilizer, which sufficiently suppresses fogging or wrinkling on the surface of a molded product even in the case of continuous production over a long period of time. The present invention relates to a chlorine-containing resin composition comprising (a) chlorine-containing resin, (b) organic acid zinc, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) β-dicarbonate Ketone compounds and/or β-diketone metal salts, and the ratio of the absorbance of the (c) oxidized polyethylene wax at 1720 cm ^{- 1} to the peak at 2930 cm ^{- 1} in the FT-IR measurement (1720 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 that can be preferably used as a material for pipes, joints, building materials, automobile parts, and the like.

Chlorine-containing resins represented by polyvinyl chloride have high flexibility and are easy to process, and also have physical properties such as flame retardancy, so they are used in agricultural films, wires, pipes, resin window frames and other applications. Various compositions having required properties have been proposed (refer to Patent Documents 1 to 4). Generally, the thermal stability of vinyl chloride resin compositions is insufficient, and a stabilizer is used in order to impart thermal stability during processing. Although Pb-based stabilizers or Sn-based stabilizers have been widely used, in recent years, the use of Ca-Zn-based stabilizers that are less toxic, ie, do not contain Pb, has been increasing in view of environmental concerns. [Prior Art Literature] [Patent Literature]

Patent Document 1: JP 2001-40217 A Patent Document 2: JP 2015-507067 A Patent Document 3: JP 9-40830 A Patent Document 4: JP 10-158451 A

[The problem to be solved by the invention]

When using "Ca-Zn-based stabilizers that have increased in recent years" to produce molded products of chlorine-containing resin compositions, if continuous production is carried out for a long time, defects such as blurring or wrinkling may occur on the surface of molded products. , and significantly reduce the problem of productivity. Sn-based stabilizers are mainly liquid stabilizers or compounds with a low melting point below the softening temperature of the resin even if they are solid. In contrast, Ca-Zn-based stabilizers contain a large amount of "inorganic substances such as hydrotalcite without melting point". The solubility and compatibility of chlorine resins are completely different. Therefore, if it is used as a Sn-based stabilizer to improve the defects of molded products, it cannot cope with this problem. Therefore, it is necessary to develop solutions corresponding to Ca-Zn-based stabilizers. method of the subject.

The present invention has been made in view of the above-mentioned situation, and an object of the present invention is to provide a chlorine-containing resin composition using a Ca-Zn-based stabilizer which can sufficiently suppress the continuous production over a long period of time. The surface of the molded product is cloudy or wrinkled. [Technical means to solve the problem]

The inventors of the present invention have conducted various studies on methods for suppressing fogging and wrinkling in the chlorine-containing resin composition using a Ca-Zn-based stabilizer. As a result, they found that if the chlorine-containing resin composition containing organic acid zinc as a stabilizer In order to further contain specific oxidized polyethylene wax, hydrotalcite, and β-diketone compounds and/or β-diketone metal salts, even in the case of continuous production over a long period of time, sufficient inhibition can be achieved. The surface of the molded article was clouded or wrinkled, and the present invention was completed.

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

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

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

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

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

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

It is preferable that the said chlorine-containing resin composition further contains (f) dipeotaerythritol hexastearate.

In the above-mentioned chlorine-containing resin composition, the content of the plasticizer with respect to the entire composition is preferably 5 wt % or less.

The above-mentioned chlorine-containing resin composition preferably further contains 30 parts by mass or less of calcium carbonate with respect to 100 parts by mass of the above-mentioned chlorine-containing resin. [Effect of invention]

The chlorine-containing resin composition of the present invention not only uses a stabilizer with low toxicity in consideration of the environment, but also sufficiently suppresses fogging or wrinkling on the surface of the molded product even in the case of continuous production over a long period of time. Therefore, it can be preferably used as a material for various molded products such as pipes, joints, building materials, and automobile parts.

Hereinafter, an example of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately changed and applied within the scope of not changing the gist of the present invention.

<Chlorine-containing resin composition> The chlorine-containing resin composition of the present invention contains (a) chlorine-containing resin, (b) organic acid zinc, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) ) β-diketone compound and/or β-diketone metal salt. One of these components may be contained, respectively, or two or more of them may be contained. Moreover, components other than these may be contained. Hereinafter, each component of (a)-(e) is demonstrated 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, but a vinyl chloride-based resin is preferable. Thereby, a molded body excellent in flexibility and flame retardancy can be obtained.

Examples of vinyl chloride-based resins include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymers, 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-urethane copolymer compound, vinyl chloride-acrylate copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene Ethylene copolymer, vinyl chloride-propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride - Copolymers such as acrylonitrile copolymer, vinyl chloride-maleimide copolymer, etc. In addition, a blend of a chlorine-containing resin and a chlorine-free resin may also be used, and the polymerization method for obtaining the vinyl chloride-based resin is not particularly limited.

[Organic acid zinc] The chlorine-containing resin composition of the present invention contains organic acid zinc to stabilize the chlorine of the chlorine-containing resin, thereby suppressing discoloration during processing or use. Zinc organic acid is a stabilizer with low toxicity that does not contain Pb. In addition, such a stabilizer that does not contain Pb and is not classified as a Sn-based stabilizer is generally referred to as a Ca-Zn-based stabilizer. The Ca-Zn-based stabilizer means not only a stabilizer containing both Ca and Zn, but also a stabilizer containing only Zn, or a stabilizer not containing both Ca and Zn and also containing no Sn. In addition, there are cases in which the Ca-Zn-based stabilizer includes a metal element other than Pb such as Sn as an auxiliary agent in addition to Ca and Zn. In the present invention, when Sn is added to a chlorine-containing resin, when its content is 0.5 parts by mass or less relative to 100 parts by mass of the chlorine-containing resin, the stabilizer is classified as a Ca-Zn-based stabilizer As for the stabilizer, when the content of Sn is more than 0.5 parts by mass, the stabilizer is classified as a Sn-based stabilizer.

The organic acid in the organic acid zinc is not particularly limited, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, 2-ethylhexanoic acid, and neodecanoic acid. , capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanoic acid, benzene Formic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzene Formic acid, cumin acid, n-propyl benzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetyloxybenzoic acid, salicylic acid, p-tert-octyl salicylic acid, tallow Monobasic organic carboxylic acids such as acid, oleic acid, linoleic acid, hypolinoleic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic 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, chlorophthalic acid, aminophthalic acid , maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, thiodipropionic acid and other dibasic organic carboxylic acids, etc.; Esters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3,5-benzenetetracarboxylic acid ( di- or tri-esters of tri- or quaternary organic carboxylic acids such as mellophanic acid), pyrometic acid, etc. Among them, higher fatty acids having 12 to 20 carbon atoms are preferred. Specifically, myristic acid, palmitic acid, isostearic acid, zinc salt of stearic acid, etc., which have suitable lubricity and compatibility with chlorine-containing resins are preferred.

Although content of the said organic acid zinc is not specifically limited, For example, it is preferable that it is 0.01 mass part or more with respect to 100 mass parts of chlorine-containing resins. 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, the appearance of the molded body is not further deteriorated, and the color tone becomes more favorable. More preferably, it is 2 parts by mass or less.

[Oxidized polyethylene wax] The chlorine-containing resin composition of the present invention contains oxidized polyethylene wax, and the ratio of the absorbance of the oxidized polyethylene wax at 1720 cm ^{- 1} to the 2930 cm ^{- 1} peak in FT-IR measurement (1720 cm ^{- 1} peak absorbance/2930 cm ^{- 1} peak absorbance) is 0.05 or more. The peak at 1720 cm ^{- 1} is the peak that occurs when the oxidation of polyethylene wax proceeds, and the peak at 2930 cm ^{- 1} is the peak of the hydrocarbon bond of polyethylene wax. By using the polyethylene wax in which the ratio of these peaks is 0.05 or more, that is, the oxidation has progressed to a certain degree or more, as the oxidized polyethylene wax, the effect of reducing the surface defects of the molded product 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 effect of improving the compatibility with the resin and suppressing the appearance defect of the molded product is more fully exhibited. The acid value of the oxidized polyethylene wax is more preferably 5 mgKOH/g or more, and more preferably 10 mgKOH/g or more. Moreover, 30 mgKOH/g or less is preferable.

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, sublimed substances and the like are reduced, and the chlorine-containing resin composition of the present invention has the effect of reducing surface defects of molded articles in terms of moldability. The melting point of the oxidized polyethylene wax is more preferably 85°C or higher, further preferably 90°C or higher. In addition, the melting point of the oxidized polyethylene wax is usually 150°C or lower.

The oxidized polyethylene wax preferably has a viscosity of 1000 cps or less at 140°C. 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 below 800 cps. More preferably, it is 500 cps or less.

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

Examples of oxidized polyethylene waxes include Hi-Wax series manufactured by Mitsui Chemicals, SANWAX series manufactured by Sanyo Chemical Industries, Viscol series manufactured by Sanyo Chemical Industries, Luvax series manufactured by Nippon Refined Wax Corporation, and Luvax series manufactured by Honeywell Corporation. Among them, AC series, etc., those satisfying the above-mentioned physical properties can be appropriately 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 relative to 100 parts by mass of the chlorine-containing resin. Thereby, the effect of suppressing the appearance defect of a molded product is exhibited more fully. More preferably, it is 0.01-1.5 mass parts, More preferably, it is 0.01-1.0 mass parts.

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

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

In the above general formula (1), the n-valent interlayer anion is not particularly limited, but is preferably selected from the group consisting of hydroxide ions (OH ⁻ ), 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, and x+y+z=1, and the ratio of x+y to z is {(x+y)/ z} is 2.2 or less. Here, what is y=0 is called Mg/Al-based hydrotalcite, and what is 0<y is called zinc-modified hydrotalcite. In the present invention, any one of these can be preferably 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, 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 absorption of the hydrotalcite is more preferably 45 ml/100 g or less, and still more preferably 40 ml/100 g or less. In addition, from the viewpoint of heat resistance, it is preferably 5 ml/100 g or more. More preferably, it is 10 ml/100 g or more.

In this specification, the oil absorption amount of a hydrotalcite-type powder is measured based on JISK5101-13-1 (2004: Refined linseed oil method).

The shape of the particle|grains of the said hydrotalcite is not specifically limited, For example, a plate shape, a spherical shape, a disk shape, etc. are mentioned. Among them, a plate or disk shape is preferable. In addition, the particle shape can be observed with a scanning electron microscope or the like.

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

In this specification, the average particle diameter can be measured as D50 using, for example, a laser diffraction particle size distribution analyzer (LA950 manufactured by HORIBA). The so-called D50 refers to the 50% cumulative particle size on a volume basis.

The specific surface area (also referred to as SSA) of the hydrotalcite is preferably, for example, 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 effect of the present invention is further improved. More preferably, it is 5 m ² /g or more, more preferably 10 m ² /g or more, and more preferably 40 m ² /g or less, and still more preferably 30 m ² /g or less. If the specific surface area is within this range, a resin composition excellent in heat resistance can be obtained.

In this specification, the specific surface area means the 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 on solid particles, and the specific surface area is measured according to the amount of adsorption. The monomolecular adsorption amount VM is obtained from the relationship between the pressure P and the adsorption amount V by the BET formula, and is determined. specific surface area. Specifically, the BET specific surface area was measured under the following conditions.

[Measurement conditions of specific surface area] Machine: Macsorb Model HM-1220 manufactured by Mounttech Co., Ltd. Adsorbed gas: nitrogen (N ₂ ) Degassing conditions of external degassing device: 105°C-15 minutes Degassing conditions of the main body of the specific surface area measuring device : 105℃－5 minutes

The particle|grains in the said hydrotalcite powder may have a coating layer. In this case, it is preferable that the physical properties of the hydrotalcite containing particles having the coating layer satisfy the above-mentioned physical properties (particle shape, average particle diameter, specific surface area, etc.). Although it does not specifically limit as a coating layer, It is preferable that it is covered by surface-treatment using a surface-treating agent.

Although it does not specifically limit as said surface treatment agent, For example, coupling agents, such as a higher fatty acid, a higher fatty acid metal salt (metal soap), an anionic surfactant, a phosphoric acid ester, a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent are mentioned. In addition, one kind or two or more kinds may be used.

More specific surface treatment agents include, for example, 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 these higher fatty acids; stearic acid; Sulfate salts of higher alcohols such as alcohol and oleyl alcohol, sulfate ester salts of polyethylene glycol ethers, amide bond sulfate ester salts, ether bond sulfonates; ester bond sulfonates, amide bond alkyl aryl sulfonic acids Anionic surfactants such as salts, ether alkyl aryl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc. or their mixtures, that is, their acid or alkali metal salts or amines Phosphate esters such as salts; vinylethoxysilane, γ-methacryloyloxypropyltrimethylsilane, vinyltris(2-methoxyethoxy)silane, γ-aminopropyltrimethoxy Silane coupling agents such as silane; isopropyl triisostearyl titanate, isopropyl tris(dioctylpyrophosphoryloxy) titanate, isopropyl tridecylbenzenesulfonyl titanate, etc. Coupling agents; alkali coupling agents such as acetoxyaluminum diisopropyl ester.

The usage amount of the above-mentioned surface treatment agent is not particularly limited, for example, it is preferable that the coating amount obtained by the surface treatment agent is 0.1 to 30 mass % relative to 100 mass % of the finally obtained hydrotalcite containing particles with a coating layer. The amount of surface treatment agent used is adjusted in the range of %. More preferably, it is the range of 0.1-20 mass %.

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

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

Although it does not specifically limit as a β-diketone compound, For example, acetone acetone, or stearyl acetyl methane, benzyl acetyl methane, dibenzyl methane, stearyl acetyl group is preferable. Benzylmethane, octylbenzylmethane, bis(4-octylbenzyl)methane, 4-methoxybenzylbenzylmethane, bis(4-carboxymethylbenzene) carboxyl) methane, 2-carboxymethylbenzyl acetidyl octyl methane, 2-benzyl cyclohexane, and other alkyl aryl aryl methanes or diaryl aryl methanes. As the β-diketone metal salt, the metal salt of the above-mentioned β-diketone compound is preferable. Although it does not specifically limit as a metal kind of a metal salt, For example, calcium, zinc, etc. are mentioned.

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 with respect to 100 parts by mass of the chlorine-containing resin. More preferably, it is 0.01-1.0 mass part.

[Mold Release Agent] In addition, the chlorine-containing resin composition of the present invention preferably contains a mold release agent. As a mold release agent, dipivalerythritol hexastearate, neopentaerythritol tetrastearate, etc. are mentioned, Among these, it is preferable to contain dipivalerythritol hexastearate. Thereby, fogging and wrinkling of the chlorine-containing resin composition of the present invention can be suppressed more sufficiently.

When the chlorine-containing resin composition of the present invention contains a mold release agent, its content is not particularly limited, but for example, it is preferably 0.01 to 5.0 parts by mass relative to 100 parts by mass of the chlorine-containing resin. More preferably, it is 0.01-2.0 mass parts.

[Filler] In addition, the chlorine-containing resin composition of the present invention preferably contains a filler. As a result, the dimensional stability of the molded article and the strength of the molded article are improved, and thus it becomes a preferable resin composition for molded articles. Fillers also function as neutralizers.

The filler is not particularly limited, and examples include inorganic powders such as inorganic salts, inorganic oxides, and inorganic hydroxides, for example, zinc, titanium, iron, cerium, barium, calcium, silicon, aluminum, magnesium, Salts, oxides, hydroxides and complex oxides of strontium, boron, zirconium, etc. Although it does not specifically limit as a salt, For example, a sulfate, a carbonate, a chloride salt, an acetate, a nitrate, etc. are mentioned. Specifically, calcium carbonate, zinc carbonate, magnesium carbonate, silicon oxide, zinc oxide, titanium oxide, cerium oxide, iron oxide, barium sulfate, strontium sulfate, magnesium sulfate, silicon oxide, aluminum oxide, magnesium oxide, silicon Zinc acid, zinc titanate, barium titanate, talc, etc., among them, 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 preferable. More preferably, it is 23 m ² /g or less, still more 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 said range, there exists a possibility that a bad influence, such as precipitation, may arise during processing.

When the said resin composition contains a filler, its content is not specifically limited, For example, it is preferable that it is 40 mass parts or less with respect to 100 mass parts of chlorine-containing resins. When it exceeds 40 mass parts, precipitation may not be suppressed. More preferably, it is 30 parts by mass or less, and still more preferably 1 to 30 parts by mass. Further more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, particularly 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 parts by mass or more. It is preferable that the content of calcium carbonate having a specific surface area of 20 m ² /g or less is within these preferable ranges.

[Other components] The chlorine-containing resin composition of the present invention may further contain other components as needed. For example, various additives such as heat-resistant adjuvants, lubricants other than the oxidized polyethylene wax of the above (c), ultraviolet absorbers, antioxidants, cross-linking adjuvants, and plasticizers can be mentioned. Various additives are not particularly limited, for example, as a heat-resistant auxiliary agent, polyol compounds such as dipeptaerythritol, or epoxy compounds such as epoxy resins can be cited; as lubricants, stearic acid monoglyceride, palmitic acid mono Glycerides, stearic acid, palmitic acid, polyethylene waxes other than the oxidized polyethylene wax of the above (c), etc.; as the ultraviolet absorber, benzophenone-based compounds, benzotriazole-based compounds, aromatic benzene compounds, etc. Formate-based compounds, etc.; as antioxidants, phenol-based compounds, etc.; Examples of the agent include dioctyl phthalate (DOP), trioctyl trimellitate (TOTM), dioctyl adipate (DOA), and the like.

In the chlorine-containing resin composition of the present invention, the content of the plasticizer relative to the entire composition is preferably 5% by weight or less. In the case of a molded product obtained from a rigid resin composition with a small content of plasticizer, poor appearance is likely to occur. Therefore, in the case where the resin composition is a hard type with a small content of the plasticizer, the effect of the present invention is more clearly exhibited. The content of the plasticizer is more preferably 1.0% by weight or less, and still more preferably 0.01% by weight or less. [Example]

In order to demonstrate this invention in detail, although an Example is given below, this invention is not limited only to these Examples.

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

(b) Zinc organic acid Zinc stearate: SZ-P (Ca-Zn-based stabilizer) manufactured by Sakai Chemical Industry Co., Ltd.

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

(d) Hydrotalcite Synthesis was performed by variously changing the molar ratios of magnesium sulfate, aluminum sulfate, and zinc sulfate and the production conditions using the production operation of hydrotalcite described in Example 4 of Japanese Patent No. 5056014. , the oil absorption and the specific surface area were measured by the following methods each time of manufacture, and the hydrotalcite-type powders described in Table 1-1 and Table 1-2 were selected.

(e) β-diketone compound, β-diketone metal salt Dibenzylmethane: 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 Sakai Chemical Industry Co., Ltd., SC-P (Ca-Zn-based stabilizer) Dipivalerythritol: manufactured by Hiroei Chemical Co., Ltd. Dipentarit 300 Polyethylene Wax: manufactured by Mitsui Chemicals Co., Ltd., Hi-Wax 220MP Ester Wax (Dipiverythritol hexastearate): manufactured by Riken Vitamin, Rikester SL-02

Examples 1-8 and Comparative Examples 1-7 The composition of each component is shown in Table 1-1 and Table 1-2. The physical properties of oxidized polyethylene wax and hydrotalcite were measured by the following measurement methods. In addition, in Table 1-1 and Table 1-2, about the obtained resin composition, the evaluation result of the wrinkle and glossiness of the surface of a molded article evaluated by the following method is also shown.

<Measurement of Physical Properties of Oxidized Polyethylene Wax> [Acid value] It was measured according to ASTM D-1386. [Density] Measured according to ASTM D-1505. [Melting point (dropping point)] Measured according to ASTM D-3954. [Viscosity at 140°C] The viscosity at 140°C was measured with a B-type viscometer (manufactured by Brookfield). [FT-IR Peak Intensity Ratio] It was measured by Fourier transform infrared spectroscopy using the following apparatus and measurement method. Manufacturer's name: Thermo Fisher Scientific Model: NICOLET 4700 Measurement method: ATR method (attenuated total reflectance method) / 1 reflection (plate used: diamond plate) Measurement procedure: (1) Not mounted on a plate Background values were determined for any item. (2) After measuring the background value, press about 1 tablespoon of the sample against the plate to measure. (3) After measuring the sample, perform "Advanced ATR Calibration", and use this as the measurement result. <Measurement of Physical Properties of Hydrotalcite> [Oil Absorption] It was measured according to JIS K5101-13-1 (2004: Refined linseed oil method).

<Molding processing> Using the above-mentioned LABO extruder (conical type 2D20C, manufactured by Toyo Seiki Co., Ltd.) having a suction and setting machine with cooling function (a device that smoothes the surface of the molded product) The resin composition was continuously extruded for 5 hours to form a pipe pipe, and was cut at fixed lengths to obtain a pipe pipe molded product. The extrusion conditions were set as follows. The temperature of the material tank starts from the position close to the input port of the raw material, and the temperature of the material tank is set to 1:175℃, the temperature of the material tank is 2:180℃, and the temperature of the material tank is 3:185℃, and the temperature of the adapter mold is set to 185℃. The mold 1 was set to 180°C, and the mold 2 was set to 205°C. As the mold, the mold for pipe pipe is used.

<Evaluation of resin composition> [Wrinkle] The state of wrinkling (that is, the state of occurrence of scratches in the tube tube molded product) obtained after a certain time elapsed from the start of extrusion molding was visually confirmed, and the Evaluation was based on the following criteria. ⊚: No scratches were observed in the formed pipe tube formed after 5 hours. ○: Scratch was observed in the formed pipe tube molded product after 3 hours. Δ: Scratch was observed in the formed pipe tube molded product after 1 hour. Í: Scratches were confirmed on the tube and tube molded product that was molded within 1 hour. [Glossiness] The state of the glossiness of the pipe tube molded article obtained after a predetermined time elapsed from the start of extrusion molding was visually confirmed, and evaluated according to the following criteria. ⊚: It was confirmed that the duct pipe molded article formed after 5 hours maintained gloss. ◯: Gloss was observed after 3 hours, but after 5 hours, it was confirmed that the formed pipe tube formed was dull and the surface of the formed pipe pipe was in a blurred state. Δ: Gloss was confirmed after 1 hour, but after 3 hours it was confirmed that the formed duct pipe formed was dull and the surface of the formed duct pipe was in a blurred state. Í: It was confirmed that it was dull immediately after forming, and the surface of the formed pipe was in a blurred state.

[表1－2]

[Table 1-1]

[Table 1-2]

From the results of Table 1-1 and Table 1-2, it was confirmed that the oxidized polyethylene wax containing the absorbance ratio of the peak at 1720 cm ^{- 1} and the peak at 2930 cm ^{- 1} in the FT-IR measurement was 0.05 or more, It can effectively suppress the occurrence of defects on the surface of the molded article of the chlorine-containing resin composition using the Ca-Zn-based stabilizer.

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Claims (9)

A chlorine-containing resin composition comprising (a) chlorine-containing resin, (b) organic acid zinc, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) β-diketone compound and/ or β-diketone metal salt, and the ratio of the absorbance of the (c) oxidized polyethylene wax at 1720cm ^-1 peak to 2930cm ^-1 peak absorbance in FT-IR measurement (1720cm ^-1 peak absorbance/2930cm ^-1 peak absorbance absorbance) is 0.05 or more. The chlorine-containing resin composition according to claim 1, wherein the acid value of the (c) oxidized polyethylene wax is 1 mgKOH/g or more. The chlorine-containing resin composition according to claim 1 or 2, wherein the density of the (c) oxidized polyethylene wax is 0.95 g/cm ³ or less. The chlorine-containing resin composition according to claim 1 or 2, wherein the melting point of the (c) oxidized polyethylene wax is 80°C or higher. The chlorine-containing resin composition according to claim 1 or 2, 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 claim 1 or 2, wherein the oil absorption of the hydrotalcite (d) is 50 ml/100 g or less. The chlorine-containing resin composition according to claim 1 or 2, wherein the chlorine-containing resin composition further contains (f) dipivalerythritol hexastearate. The chlorine-containing resin composition according to claim 1 or 2, wherein the content of the plasticizer relative to the entire composition is 5% by weight or less. The chlorine-containing resin composition according to claim 1 or 2, further comprising 30 parts by mass or less of calcium carbonate with respect to 100 parts by mass of the chlorine-containing resin.