WO2019087479A1 - Chlorine-containing resin composition - Google Patents

Chlorine-containing resin composition Download PDF

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Publication number
WO2019087479A1
WO2019087479A1 PCT/JP2018/027947 JP2018027947W WO2019087479A1 WO 2019087479 A1 WO2019087479 A1 WO 2019087479A1 JP 2018027947 W JP2018027947 W JP 2018027947W WO 2019087479 A1 WO2019087479 A1 WO 2019087479A1
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Prior art keywords
chlorine
containing resin
resin composition
acid
polyethylene wax
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PCT/JP2018/027947
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French (fr)
Japanese (ja)
Inventor
誠 大出水
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堺化学工業株式会社
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Publication of WO2019087479A1 publication Critical patent/WO2019087479A1/en
Priority to PH12020550572A priority Critical patent/PH12020550572A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms

Definitions

  • the present invention relates to chlorine-containing resin compositions. More specifically, the present invention relates to a chlorine-containing resin composition that can be suitably used as a material for pipes, joints, building materials, automobile parts and the like.
  • Chlorine-containing resins represented by polyvinyl chloride are used for various applications such as agricultural films, electric wires, pipes, resin window frames, etc. because they have high flexibility, are easily processed, and have physical properties such as flame retardancy.
  • Various compositions have been proposed according to the required properties (see Patent Documents 1 to 4).
  • the vinyl chloride resin composition is insufficient in heat stability, and a stabilizer is used to impart heat stability during processing.
  • Pb-based stabilizers and Sn-based stabilizers have been widely used, but in recent years, the use of less toxic Pb-free Ca—Zn-based stabilizers has increased in consideration of environmental considerations.
  • JP 2001-40217 A JP-A-2015-507067 JP 9-40830 A Unexamined-Japanese-Patent No. 10-158451
  • the present invention has been made in view of the above-mentioned present situation, and even when a Ca-Zn-based stabilizer is used and continuous production is performed for a long time, occurrence of blur or streaking on the surface of a molded article is sufficient. It is an object of the present invention to provide a chlorine-containing resin composition suppressed to
  • the inventors of the present invention have investigated various methods for suppressing the occurrence of blurring and streaking of a chlorine-containing resin composition using a Ca-Zn-based stabilizer, and have found that a chlorine-containing resin composition containing an organic acid zinc as a stabilizer. Further, when specific oxidized polyethylene wax, hydrotalcite, and ⁇ -diketone compound and / or ⁇ -diketo metal salt are contained, even if continuous production is performed for a long time, the surface of the molded article becomes blurred or streaked. It has been found that the occurrence of can be sufficiently suppressed, and the present invention has been completed.
  • the present invention comprises (a) chlorine-containing resin, (b) zinc organic acid, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) ⁇ -diketone compound and / or ⁇ -diketo metal salt wherein the said (c) oxidized polyethylene wax, the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement (1720 cm -1 peak absorbance / 2930 cm -1 peak absorbance) 0.05 It is the chlorine containing resin composition which is the above.
  • the (c) oxidized polyethylene wax preferably has an acid value of 1 mg KOH / g or more.
  • the (c) oxidized polyethylene wax preferably has a density of 0.95 g / cm 3 or less.
  • the (c) oxidized polyethylene wax preferably has a melting point of 80 ° C. or higher.
  • the (c) oxidized polyethylene wax preferably has a melt viscosity at 140 ° C. of 1,000 cps or less.
  • the (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 content of the plasticizer relative to the whole composition is preferably 5% by weight or less.
  • the chlorine-containing resin composition preferably further contains calcium carbonate in an amount of 30 parts by mass or less based on 100 parts by mass of the chlorine-containing resin.
  • the chlorine-containing resin composition of the present invention uses a stabilizer with low toxicity in consideration of the environment, the occurrence of streaks and streaks on the surface of the molded article is sufficient even when continuous production is performed for a long time Since it is suppressed to, it can be suitably used as a material of various molded articles such as pipes, joints, building materials, automobile parts and the like.
  • the present invention is not limited only to the following descriptions, and it can change suitably and can apply it in the range which does not change the gist of the present invention.
  • the chlorine-containing resin composition of the present invention comprises (a) chlorine-containing resin, (b) organic acid zinc, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) ⁇ -diketone compound and / or Contains ⁇ -diketo metal salts.
  • Each of these components may contain 1 type, and may contain 2 or more types. Moreover, components other than these may be included.
  • the components (a) to (e) will be described in order below.
  • the chlorine-containing resin is not particularly limited as long as it is a resin (polymer) containing a chlorine atom, but a vinyl chloride resin is preferable. Thereby, the molded object which is excellent in a softness
  • vinyl chloride resins include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, etc .; vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer Combination, 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 , Vinyl chloride-acrylic ester copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, chloride Vinyl-chlorinated propylene copo
  • Organic acid zinc By containing the organic acid zinc, the chlorine of the chlorine-containing resin is stabilized, and the color change of the chlorine-containing resin composition of the present invention can be suppressed during processing and during use.
  • Organic acid zinc is a Pb-free stabilizer with low toxicity.
  • such a stabilizer which does not contain Pb and which is not classified as a Sn-based stabilizer is generally referred to as a Ca--Zn-based stabilizer.
  • the Ca-Zn-based stabilizer does not mean only those containing both Ca and Zn, and also includes a stabilizer containing only Zn and a stabilizer containing neither Ca and Zn nor Sn.
  • a stabilizer containing a metal element other than Pb such as Sn as an auxiliary agent may be included in the Ca-Zn-based stabilizer.
  • Sn a metal element other than Pb
  • its stabilizer is Ca.
  • 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, caproic acid, enanthate, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-t-butylbenzoic acid, dimethylhydroxybenzoic acid 3,5-di-t-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, Acetoxybenz
  • the content of the organic acid zinc is not particularly limited, and for example, the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the chlorine-containing resin. Thereby, discoloration can be suppressed. More preferably, it is 0.1 parts by mass or more. Moreover, it is preferable that it is 5 mass parts or less, and, thereby, heat resistance can be improved more, the external appearance of a molded object will not fall more, and a color tone will become more favorable. More preferably, it is 2 parts by mass or less.
  • the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement (1720 cm -1 peak absorbance / 2930 cm -1 peak absorbance) is 0.05 or more It contains some oxidized polyethylene wax.
  • the peak at 1720 cm -1 is a peak that appears as the oxidation of polyethylene wax proceeds, and the peak at 2930 cm -1 is a peak of hydrocarbon bonds indicating polyethylene wax.
  • the oxidized polyethylene wax preferably has an acid value of 1 mg KOH / g or more.
  • the acid value of the oxidized polyethylene wax is more preferably 5 mg KOH / g or more, still more preferably 10 mg KOH / g or more. Moreover, it is preferable that it is 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 moldability 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 more, the sublimate and the like decrease, and the chlorine-containing resin composition of the present invention can exhibit the effect of reducing the surface defects of the molded product in the molding processability.
  • the melting point of the oxidized polyethylene wax is more preferably 85 ° C. or more, still more preferably 90 ° C. or more.
  • the melting point of the oxidized polyethylene wax is usually 150 ° C. or less.
  • the oxidized polyethylene wax preferably has a viscosity of 1,000 cps or less at 140.degree. When the viscosity at 140 ° C. is 1000 cps or less, the chlorine-containing resin composition of the present invention is excellent in molding processability.
  • the viscosity at 140 ° C. of the oxidized polyethylene wax is preferably 800 cps or less. More preferably, it is 500 cps or less.
  • the acid value, density, melting point and viscosity at 140 ° C. of the oxidized polyethylene wax are all measured by the methods described in the examples.
  • polyethylene oxide wax for example, high wax series made by Mitsui Chemicals, Sanwax series made by Sanyo Chemical Industries, Viscor series made by Sanyo Chemical Industries, Luvacs series made by Nippon Seiwa Co., AC series made by Honeywell, etc. Among them, those which satisfy 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 with respect to 100 parts by mass of the chlorine-containing resin. Thereby, the effect which suppresses the appearance defect of a molded article is exhibited more fully. More preferably, it is 0.01 to 1.5 parts by mass, and still more preferably 0.01 to 1.0 parts by mass.
  • the hydrotalcite contained in the chlorine-containing resin composition of the present invention is not particularly limited, but one containing magnesium element (Mg) and / or zinc element (Zn) and aluminum element (Al) is preferable.
  • the following general formula (1) ⁇ (Mg) x (Zn) y ⁇ (Al) z (OH) 2 (A n-) x / n ⁇ mH 2 O (1)
  • a n ⁇ represents an n-valent interlayer anion.
  • the ratio of ⁇ x + y) / z ⁇ of x + y to z is 2.2 or less
  • n and m are numbers satisfying 1 ⁇ n ⁇ 4 and 0 ⁇ m, respectively. It is represented by.).
  • the heat resistance and thermal stability of the chlorine-containing resin composition are further improved.
  • the general formula (1) it is not particularly restricted but includes n-valent interlayer anion, in view of reactivity and environmental load reduction, the hydroxide ion (OH -), carbonate ions (CO 3 2-) and sulfate ions At least one selected from the group consisting of (SO 4 2- ) is preferred. Among them, carbonate ion is preferable.
  • zinc modified hydrotalcite any of these can be suitably used.
  • the ratio ⁇ (x + y) / z ⁇ of x + y to 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 absorption of hydrotalcite is more preferably 45 ml / 100 g or less, still more preferably 40 ml / 100 g or less. Moreover, it is preferable that it is 5 ml / 100 g or more from a heat resistant viewpoint. More preferably, it is 10 ml / 100 g or more.
  • the oil absorption 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 plate, sphere, and disc. Among them, a plate or a disc is preferable. The particle shape can be observed by a scanning electron microscope or the like.
  • the average particle diameter of the hydrotalcite particles is preferably, for example, 0.1 ⁇ m or more and 2.0 ⁇ m or less. Thereby, the dispersibility to chlorine containing resin improves and the effect of this invention improves more. More preferably, it is 0.3 ⁇ m or more, and more preferably, 1.5 ⁇ m or less.
  • the average particle size can be measured as D50 using, for example, a laser diffraction particle size distribution measuring apparatus (LA950 manufactured by HORIBA).
  • D50 means 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 to chlorine containing resin improves and the effect of this invention improves more. More preferably, it is 5 m 2 / g or more, further preferably 10 m 2 / g or more, and more preferably 40 m 2 / g or less, more preferably 30 m 2 / g or less.
  • the resin composition excellent in heat resistance can be obtained as a specific surface area is this range.
  • 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 from the amount adsorbed. From the relationship between pressure P and adsorption amount V, the monomolecular adsorption amount VM is calculated by the BET equation.
  • the specific surface area is determined by finding it. Specifically, the BET specific surface area is measured under the following conditions.
  • the particles in the powder may have a coating layer.
  • the physical properties of the hydrotalcite containing the particles having the coating layer satisfy the above-mentioned physical properties (particle shape, average particle size, specific surface area, etc.).
  • it does not specifically limit as a coating layer, It is preferable that it surface-treats and coats using a surface treating agent.
  • the surface treatment agent is not particularly limited, and, for example, higher fatty acids, higher fatty acid metal salts (metal soaps), anionic surfactants, phosphoric esters, silane coupling agents, titanium coupling agents, aluminum coupling agents, etc. Coupling agents are mentioned. In addition, 1 type or 2 types or more can be used.
  • More specific surface treatment agents are, for example, higher fatty acids such as stearic acid, oleic acid, erucic acid, palmitic acid and lauric acid, metal salts such as lithium salts, sodium salts and potassium salts of these higher fatty acids; stearyl alcohol , Sulfuric acid ester salts of higher alcohols such as oleyl alcohol, sulfuric acid ester salts of polyethylene glycol ether, amide bond sulfuric acid ester salts, ether bond sulfonates; ester bond sulfonates, amide bond alkyl aryl sulfonates, ether bond alkyl aryl sulfonic acid Anionic surfactants such as salts; mono- or diesters of orthophosphoric acid with oleyl alcohol, stearyl alcohol etc.
  • higher fatty acids such as stearic acid, oleic acid, erucic acid, palmitic acid and lauric acid
  • metal salts such as lithium salts,
  • phosphates such as acid type or alkali metal salts or amine salts thereof; Silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, silane coupling agents such as ⁇ -aminopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl Examples include titanium coupling agents such as tridecyl benzene sulfonyl titanate; and alkaline coupling agents such as acetoalkoxyaluminum diisopropylate.
  • the amount of the surface treatment agent to be used is not particularly limited.
  • the amount of the surface treatment agent coated is 0.1 to 30% by mass with respect to 100% by mass of hydrotalcite containing particles having a finally obtained coated layer. It is preferable to adjust the amount of the surface treatment agent to be in the range of More preferably, it is in the range of 0.1 to 20% by mass.
  • the content of the hydrotalcite is, for example, preferably 0.05 parts by mass or more, and preferably 10 parts by mass or less with respect to 100 parts by mass of the chlorine-containing resin. This further improves the heat resistance and the heat stability. More preferably, it is 0.1 parts by mass or more, more preferably 8 parts by mass or less, and still more preferably 5 parts by mass or less.
  • the chlorine-containing resin composition of the present invention can also improve the colorability at the time of molding by containing the ⁇ -diketone compound and / or the ⁇ -diketo metal salt.
  • the ⁇ -diketone compound is not particularly limited.
  • Alkanoylaroylmethane such as methane, bis (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, 2-benzoylcyclohexane and the like and diaroylmethane are preferred.
  • metal salts of the above-mentioned ⁇ -diketone compounds are preferable.
  • the metal species of the metal salt is not particularly limited, and examples thereof include calcium and zinc.
  • the content of the ⁇ -diketone compound and / or the ⁇ -diketo metal salt in the above 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 to 1.0 parts by mass.
  • the chlorine-containing resin composition of the present invention preferably also contains a release agent.
  • the mold release agent include dipentaerythritol hexastearate and pentaerythritol tetrastearate. Among these, it is preferable to include dipentaerythritol hexastearate. This makes it possible to more sufficiently suppress the occurrence of lightening and streaking of the chlorine-containing resin composition of the present invention.
  • the content thereof is not particularly limited.
  • the content is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the chlorine-containing resin . More preferably, it is 0.01 to 2.0 parts by mass.
  • the chlorine-containing resin composition of the present invention preferably also contains a filler.
  • a filler As a result, the dimensional stability of the molded product and the strength of the molded product are improved, so that the resin composition is preferable for molded product applications.
  • the filler also functions as a neutralizing agent.
  • the filler is not particularly limited, and examples thereof include inorganic powders such as inorganic salts, inorganic oxides and inorganic hydroxides, and examples thereof include zinc, titanium, iron, cerium, barium, calcium, silicon, aluminum, magnesium, strontium And salts such as boron and zirconium, oxides, hydroxides and complex oxides.
  • the salts are not particularly limited, and examples thereof include sulfates, carbonates, chlorides, acetates and nitrates.
  • calcium carbonate, zinc carbonate, magnesium carbonate, silica, zinc oxide, titanium oxide, cerium oxide, cerium oxide, iron oxide, barium sulfate, strontium sulfate, magnesium sulfate, silicon oxide, aluminum oxide, magnesium oxide, silicic acid Zinc, zinc titanate, barium titanate, talc and the like can be mentioned, among which calcium carbonate is preferred.
  • one having a specific surface area (BET specific surface area) of less than 25 m 2 / g is preferable. More preferably, it is 23 m 2 / g or less, 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. If the above range is exceeded, there is a possibility that adverse effects such as plate out may occur during processing.
  • the 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 resin. If it exceeds 40 parts by mass, plate out may not be suppressed.
  • the amount is more preferably 30 parts by mass or less, still more preferably 1 to 30 parts by mass. Still 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, still more preferably 3 It is more than mass part.
  • the content of calcium carbonate having a specific surface area of 20 m 2 / g or less is within these preferable ranges.
  • the chlorine-containing resin composition of the present invention may further contain other components as needed.
  • various additives such as a heat-resistant auxiliary agent, a lubricant other than the oxidized polyethylene wax of the above (c), an ultraviolet light absorber, an antioxidant, a crosslinking auxiliary agent, a plasticizer and the like can be mentioned.
  • the additives are not particularly limited, but examples thereof include polyhydric alcohol compounds such as dipentalithitol and epoxy compounds such as epoxy resin as a heat-resistant assistant, and monoglycerides of stearic acid, monoglycerides of palmitic acid and stearin as lubricants.
  • UV absorbers include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds etc., and as antioxidants
  • crosslinking aid include trimethylolpropane trimethacrylate and dipentaerythritol hexaacrylate.
  • plasticizer include dioctyl phthalate (DOP) and trioctyl trimellime.
  • TOTM Over preparative
  • DOA dioctyl adipate
  • the chlorine-containing resin composition of the present invention preferably has a plasticizer content of 5% by weight or less based on the entire composition. Defective appearance is apt to occur in the case of a molded product obtained from a hard resin composition having a small content of plasticizer. Therefore, when the resin composition is a hard type having a small content of a plasticizer, the effects of the present invention will be more significantly exhibited.
  • the content of the plasticizer is more preferably 1.0% by weight or less, still more preferably 0.01% by weight or less.
  • Examples 1 to 8 and Comparative Examples 1 to 7 Physical properties of the oxidized polyethylene wax and hydrotalcite used in the examples and comparative examples, and the composition of each component of the resin composition prepared by containing the oxidized polyethylene wax and the hydrotalcite are shown in Table 1-1, Table 1 -2 shown. Physical properties of oxidized polyethylene wax and hydrotalcite were measured by the following measuring methods. Further, in Table 1-1 and Table 1-2, evaluation results of streaking and gloss of the surface of a molded product, which were evaluated by the following method, of the obtained resin composition are also shown.
  • Measurement method ATR method / single reflection (use plate: diamond prism plate) Measurement procedure: (1) Measure the background without putting anything on the plate (2) After the background measurement, press the sample about a teaspoon on the plate and 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] It was measured in accordance with JIS K5101-13-1 (2004: refined linseed oil method).
  • Table 1-1 the results in Table 1-2, that the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement comprises oxidized polyethylene wax is 0.05 or more, Ca It has been confirmed that the generation of defects on the surface of a molded article of a chlorine-containing resin composition using a Zn-based stabilizer can be effectively suppressed.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention provides a chlorine-containing resin composition which, even when containing a Ca-Zn type stabilizer and used in long-term continuous production, gives molded articles sufficiently inhibited from having surface irregularities or streaks. The present invention relates to a chlorine-containing resin composition which comprises (a) a chlorine-containing resin, (b) an organic acid zinc salt, (c) an oxidized polyethylene wax, (d) hydrotalcite, and (e) a β-diketone compound and/or a β-diketo-metal salt, wherein the oxidized polyethylene wax (c), in an examination by FT-IR spectroscopy, has a peak at 1,720 cm-1 and a peak at 2,930 cm-1, the absorbance ratio between the peaks, (absorbance at 1,720 cm-1 peak)/(absorbance at 2,930 cm-1 peak), being 0.05 or higher.

Description

塩素含有樹脂組成物Chlorine-containing resin composition
本発明は、塩素含有樹脂組成物に関する。より詳しくは、パイプ、継手、建材、自動車部品等の材料として好適に用いることができる塩素含有樹脂組成物に関する。 The present invention relates to chlorine-containing resin compositions. More specifically, the present invention relates to a chlorine-containing resin composition that can be suitably used as a material for pipes, joints, building materials, automobile parts and the like.
ポリ塩化ビニルに代表される塩素含有樹脂は、柔軟性が高く加工しやすいうえ、難燃性等の物性も有するため、農業用フィルム、電線、パイプ、樹脂窓枠等の多様な用途に使用されており、求められる特性に応じた種々の組成物が提案されている（特許文献１～４参照）。一般に塩化ビニル樹脂組成物は熱安定性が充分でなく、加工時の熱安定性付与のために安定剤が使用される。従来は、Ｐｂ系安定剤やＳｎ系の安定剤が広く使用されてきたが、近年は環境への配慮からより低毒性のＰｂを含まないＣａ－Ｚｎ系安定剤の使用が増加してきている。 Chlorine-containing resins represented by polyvinyl chloride are used for various applications such as agricultural films, electric wires, pipes, resin window frames, etc. because they have high flexibility, are easily processed, and have physical properties such as flame retardancy. Various compositions have been proposed according to the required properties (see Patent Documents 1 to 4). In general, the vinyl chloride resin composition is insufficient in heat stability, and a stabilizer is used to impart heat stability during processing. Conventionally, Pb-based stabilizers and Sn-based stabilizers have been widely used, but in recent years, the use of less toxic Pb-free Ca—Zn-based stabilizers has increased in consideration of environmental considerations.
特開２００１－４０２１７号公報JP 2001-40217 A 特表２０１５－５０７０６７号公報JP-A-2015-507067 特開平９－４０８３０号公報JP 9-40830 A 特開平１０－１５８４５１号公報Unexamined-Japanese-Patent No. 10-158451
近年使用が増えているＣａ－Ｚｎ系安定剤を使用して塩素含有樹脂組成物の成形品を生産した場合、長時間に及ぶ連続生産を行うと、成形品表面にかすれや筋引き等の不良が発生するようになり、著しく生産性を低下させるという課題がある。Ｓｎ系安定剤は主として液状安定剤であったり、固体でも樹脂軟化温度以下の低融点化合物であるのに対し、Ｃａ－Ｚｎ系安定剤は、融点を有さないハイドロタルサイト等の無機物も多く含有するものであって、塩素含有樹脂に対する溶解度や相溶性が全く異なるため、Ｓｎ系安定剤において成形品の不良を改善するために使用される方法を転用することではこの課題に対応できず、Ｃａ－Ｚｎ系安定剤に応じた課題解決方法を開発する必要がある。 When a molded product of a chlorine-containing resin composition is produced using a Ca-Zn-based stabilizer, which has been increasingly used in recent years, defects such as blur or streaking on the surface of the molded product when continuous production is performed over a long period of time There is a problem in that the productivity is reduced significantly. While Sn-based stabilizers are mainly liquid stabilizers and low-melting compounds which are solid or lower than the resin softening temperature, Ca-Zn-based stabilizers also contain many inorganic substances such as hydrotalcite which do not have melting points. Since it contains and the solubility and compatibility with the chlorine-containing resin are completely different, this problem can not be dealt with by diverting the method used to improve the defect of the molded product in the Sn-based stabilizer, It is necessary to develop a solution to the problem according to the Ca-Zn stabilizer.
本発明は、上記現状に鑑みてなされたものであり、Ｃａ－Ｚｎ系安定剤を使用し、かつ、長時間に及ぶ連続生産を行った場合でも成形品表面のかすれや筋引きの発生が充分に抑制された塩素含有樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above-mentioned present situation, and even when a Ca-Zn-based stabilizer is used and continuous production is performed for a long time, occurrence of blur or streaking on the surface of a molded article is sufficient. It is an object of the present invention to provide a chlorine-containing resin composition suppressed to
本発明者は、Ｃａ－Ｚｎ系安定剤を用いた塩素含有樹脂組成物のかすれや筋引きの発生を抑制する方法について種々検討したところ、有機酸亜鉛を安定剤として含む塩素含有樹脂組成物を、更に特定の酸化ポリエチレンワックス、ハイドロタルサイト、並びに、β－ジケトン化合物及び／又はβ－ジケト金属塩を含むものとすると、長時間に及ぶ連続生産を行った場合でも成形品表面のかすれや筋引きの発生を充分に抑制することができることを見出し、本発明を完成するに至った。 The inventors of the present invention have investigated various methods for suppressing the occurrence of blurring and streaking of a chlorine-containing resin composition using a Ca-Zn-based stabilizer, and have found that a chlorine-containing resin composition containing an organic acid zinc as a stabilizer. Further, when specific oxidized polyethylene wax, hydrotalcite, and β-diketone compound and / or β-diketo metal salt are contained, even if continuous production is performed for a long time, the surface of the molded article becomes blurred or streaked. It has been found that the occurrence of can be sufficiently suppressed, and the present invention has been completed.
すなわち本発明は、（ａ）塩素含有樹脂、（ｂ）有機酸亜鉛、（ｃ）酸化ポリエチレンワックス、（ｄ）ハイドロタルサイト、並びに、（ｅ）β－ジケトン化合物及び／又はβ－ジケト金属塩を含み、該（ｃ）酸化ポリエチレンワックスは、ＦＴ－ＩＲ測定における１７２０ｃｍ－１のピークと２９３０ｃｍ－１のピークとの吸光度の比（１７２０ｃｍ－１ピーク吸光度／２９３０ｃｍ－１ピーク吸光度）が０．０５以上である塩素含有樹脂組成物である。 That is, the present invention comprises (a) chlorine-containing resin, (b) zinc organic acid, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) β-diketone compound and / or β-diketo metal salt wherein the said (c) oxidized polyethylene wax, the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement (1720 cm -1 peak absorbance / 2930 cm -1 peak absorbance) 0.05 It is the chlorine containing resin composition which is the above.
上記（ｃ）酸化ポリエチレンワックスは、酸価が１ｍｇＫＯＨ／ｇ以上であることが好ましい。 The (c) oxidized polyethylene wax preferably has an acid value of 1 mg KOH / g or more.
上記（ｃ）酸化ポリエチレンワックスは、密度が０．９５ｇ／ｃｍ３以下であることが好ましい。 The (c) oxidized polyethylene wax preferably has a density of 0.95 g / cm 3 or less.
上記（ｃ）酸化ポリエチレンワックスは、融点が８０℃以上であることが好ましい。 The (c) oxidized polyethylene wax preferably has a melting point of 80 ° C. or higher.
上記（ｃ）酸化ポリエチレンワックスは、１４０℃での溶融粘度が１０００ｃｐｓ以下であることが好ましい。 The (c) oxidized polyethylene wax preferably has a melt viscosity at 140 ° C. of 1,000 cps or less.
上記（ｄ）ハイドロタルサイトは、吸油量が５０ｍｌ／１００ｇ以下であることが好ましい。 The (d) hydrotalcite preferably has an oil absorption of 50 ml / 100 g or less.
上記塩素含有樹脂組成物は、更に（ｆ）ジペンタエリスリトールヘキサステアレートを含むことが好ましい。 The chlorine-containing resin composition preferably further contains (f) dipentaerythritol hexastearate.
上記塩素含有樹脂組成物は、組成物全体に対する可塑剤の含有量が５重量％以下であることが好ましい。 The content of the plasticizer relative to the whole composition is preferably 5% by weight or less.
上記塩素含有樹脂組成物は、更に炭酸カルシウムを上記塩素含有樹脂１００質量部に対して３０質量部以下含有することが好ましい。 The chlorine-containing resin composition preferably further contains calcium carbonate in an amount of 30 parts by mass or less based on 100 parts by mass of the chlorine-containing resin.
本発明の塩素含有樹脂組成物は、環境に配慮した低毒性の安定剤を使用したものでありながら、長時間に及ぶ連続生産を行った場合でも成形品表面のかすれや筋引きの発生が充分に抑制されたものであることから、パイプ、継手、建材、自動車部品等の各種成形品の材料として好適に使用することができる。 Although the chlorine-containing resin composition of the present invention uses a stabilizer with low toxicity in consideration of the environment, the occurrence of streaks and streaks on the surface of the molded article is sufficient even when continuous production is performed for a long time Since it is suppressed to, it can be suitably used as a material of various molded articles such as pipes, joints, building materials, automobile parts and the like.
以下、本発明の一例について具体的に説明するが、本発明は以下の記載のみに限定されるものではなく、本発明の要旨を変更しない範囲で適宜変更して適用することができる。 Hereinafter, although an example of the present invention is explained concretely, the present invention is not limited only to the following descriptions, and it can change suitably and can apply it in the range which does not change the gist of the present invention.
＜塩素含有樹脂組成物＞
本発明の塩素含有樹脂組成物は、（ａ）塩素含有樹脂、（ｂ）有機酸亜鉛、（ｃ）酸化ポリエチレンワックス、（ｄ）ハイドロタルサイト、並びに、（ｅ）β－ジケトン化合物及び／又はβ－ジケト金属塩を含む。これらの成分はそれぞれ１種を含んでいてもよく、２種以上を含んでいてもよい。また、これら以外の成分を含んでいてもよい。以下に、（ａ）～（ｅ）の各成分について順に説明する。 <Chlorine-containing resin composition>
The chlorine-containing resin composition of the present invention comprises (a) chlorine-containing resin, (b) organic acid zinc, (c) oxidized polyethylene wax, (d) hydrotalcite, and (e) β-diketone compound and / or Contains β-diketo metal salts. Each of these components may contain 1 type, and may contain 2 or more types. Moreover, components other than these may be included. The components (a) to (e) will be described in order below.
［塩素含有樹脂］
塩素含有樹脂は、塩素原子を含む樹脂（重合体）である限り特に限定されないが、塩化ビニル系樹脂が好ましい。これにより、柔軟性や難燃性に優れる成形体が得られる。 [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 resin is preferable. Thereby, the molded object which is excellent in a softness | flexibility or a flame retardance is obtained.
塩化ビニル系樹脂としては、例えば、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン等の単独重合体；塩化ビニル－酢酸ビニル共重合体、塩化ビニル－エチレン－酢酸ビニル共重合体、塩化ビニル－エチレン共重合体、塩化ビニル－プロピレン共重合体、塩化ビニル－スチレン共重合体、塩化ビニル－イソブチレン共重合体、塩化ビニル－塩化ビニリデン共重合体、塩化ビニル－ウレタン共重合体、塩化ビニル－アクリル酸エステル共重合体、塩化ビニル－スチレン－無水マレイン酸共重合体、塩化ビニル－スチレン－アクリロニトリル共重合体、塩化ビニル－ブタジエン共重合体、塩化ビニル－イソプレン共重合体、塩化ビニル－塩素化プロピレン共重合体、塩化ビニル－塩化ビニリデン－酢酸ビニル共重合体、塩化ビニル－マレイン酸エステル共重合体、塩化ビニル－メタクリル酸エステル共重合体、塩化ビニル－アクリロニトリル共重合体、塩化ビニル－マレイミド共重合体等の共重合体；等が挙げられる。なお、塩素含有樹脂と塩素非含有樹脂とのブレンド品を使用してもよいし、また塩化ビニル系樹脂を得るための重合方法は特に限定されない。 Examples of vinyl chloride resins include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, etc .; vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer Combination, 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 , Vinyl chloride-acrylic ester copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, chloride Vinyl-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate Polymers, vinyl chloride - maleic acid ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - copolymers such as maleimide copolymer; and the like. A blend of a chlorine-containing resin and a non-chlorine-containing resin may be used, and the polymerization method for obtaining a vinyl chloride resin is not particularly limited.
［有機酸亜鉛］
本発明の塩素含有樹脂組成物は、有機酸亜鉛を含むことで、塩素含有樹脂の塩素が安定化され、加工時、また使用時の変色を抑制することができる。
有機酸亜鉛は、Ｐｂを含まない毒性の低い安定剤である。なお、このようなＰｂを含まない安定剤であって、Ｓｎ系安定剤に分類されないものを一般にＣａ－Ｚｎ系安定剤と称する。Ｃａ－Ｚｎ系安定剤はＣａとＺｎの両方を含むもののみを意味せず、Ｚｎのみを含む安定剤やＣａとＺｎのいずれも含まず、かつＳｎも含まない安定剤も含まれる。また、ＣａとＺｎの他に、助剤としてＳｎ等のＰｂ以外の金属元素を含む安定剤もＣａ－Ｚｎ系安定剤に含まれることがある。
本発明においては、Ｓｎを含んでいても、塩素含有樹脂に添加した場合にその含有量が塩素含有樹脂１００質量部に対して、０．５質量部以下となる場合にはその安定剤をＣａ－Ｚｎ系安定剤、Ｓｎの含有量が０．５質量部より多くなる場合にはその安定剤をＳｎ系安定剤と分類する。 [Organic acid zinc]
By containing the organic acid zinc, the chlorine of the chlorine-containing resin is stabilized, and the color change of the chlorine-containing resin composition of the present invention can be suppressed during processing and during use.
Organic acid zinc is a Pb-free stabilizer with low toxicity. In addition, such a stabilizer which does not contain Pb and which is not classified as a Sn-based stabilizer is generally referred to as a Ca--Zn-based stabilizer. The Ca-Zn-based stabilizer does not mean only those containing both Ca and Zn, and also includes a stabilizer containing only Zn and a stabilizer containing neither Ca and Zn nor Sn. In addition to Ca and Zn, a stabilizer containing a metal element other than Pb such as Sn as an auxiliary agent may be included in the Ca-Zn-based stabilizer.
In the present invention, even if Sn is contained, when it is added to a chlorine-containing resin and its content is 0.5 parts by mass or less with respect to 100 parts by mass of the chlorine-containing resin, its stabilizer is Ca. When the content of the Zn-based stabilizer and Sn is more than 0.5 parts by mass, the stabilizer is classified as a Sn-based stabilizer.
有機酸亜鉛における有機酸としては特に限定されないが、例えば、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、２－エチルヘキシル酸、ネオデカン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、パルミチン酸、イソステアリン酸、ステアリン酸、１２－ヒドロキシステアリン酸、ベヘニン酸、モンタン酸、安息香酸、モノクロル安息香酸、ｐ－ｔ－ブチル安息香酸、ジメチルヒドロキシ安息香酸、３，５－ジ－ｔ－ブチル－４－ヒドロキシ安息香酸、トルイル酸、ジメチル安息香酸、エチル安息香酸、クミン酸、ｎ－プロピル安息香酸、アミノ安息香酸、Ｎ，Ｎ－ジメチルアミノ安息香酸、アセトキシ安息香酸、サリチル酸、ｐ－ｔ－オクチルサリチル酸、エライジン酸、オレイン酸、リノール酸、リノレイン酸、チオグリコール酸、メルカプトプロピオン酸、オクチルメルカプトプロピオン酸等の１価有機カルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、ヒドロキシフタル酸、クロルフタル酸、アミノフタル酸、マレイン酸、フマール酸、シトラコン酸、メタコン酸、イタコン酸、アコニット酸、チオジプロピオン酸等の２価有機カルボン酸；等の他、２価有機カルボン酸のモノエステル又はモノアミド化合物、ブタントリカルボン酸、ブタンテトラカルボン酸、ヘミメリット酸、トリメリット酸、メロファン酸、ピロメリット酸等の３価又は４価の有機カルボン酸のジ又はトリエステル；等が挙げられる。中でも、炭素数１２～２０の高級脂肪酸が好ましい。具体的には、適度な滑性と塩素含有樹脂との相溶性がある、ミリスチン酸、パルミチン酸、イソステアリン酸、ステアリン酸の亜鉛塩等が好ましい。 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, enanthate, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-t-butylbenzoic acid, dimethylhydroxybenzoic acid 3,5-di-t-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, Acetoxybenzoic acid, salicylic acid, p-t-octylsalicylic acid, Ella Monovalent organic carboxylic acids such as dioic acid, oleic acid, linoleic acid, linolenic 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, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid Etc., monoesters or monoamide compounds of divalent organic carboxylic acids, butane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid, trimellitic acid, merophonic acid, pyromellitic acid, etc. 3 Or tetravalent organic carboxylic acid Ester; and the like. Among them, higher fatty acids having 12 to 20 carbon atoms are preferable. Specifically, myristic acid, palmitic acid, isostearic acid, zinc salts of stearic acid, and the like, which have appropriate lubricity and compatibility with chlorine-containing resins, are preferable.
上記有機酸亜鉛の含有量は特に限定されず、例えば、塩素含有樹脂１００質量部に対して０．０１質量部以上であることが好ましい。これにより、変色を抑制することができる。より好ましくは０．１質量部以上である。また、５質量部以下であることが好ましく、これにより、耐熱性をより高めることができ、成形体の外観がより低下せず、色調もより良好なものとなる。より好ましくは２質量部以下である。 The content of the organic acid zinc is not particularly limited, and for example, the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the chlorine-containing resin. Thereby, discoloration can be suppressed. More preferably, it is 0.1 parts by mass or more. Moreover, it is preferable that it is 5 mass parts or less, and, thereby, heat resistance can be improved more, the external appearance of a molded object will not fall more, and a color tone will become more favorable. More preferably, it is 2 parts by mass or less.
［酸化ポリエチレンワックス］
本発明の塩素含有樹脂組成物は、ＦＴ－ＩＲ測定における１７２０ｃｍ－１のピークと２９３０ｃｍ－１のピークとの吸光度の比（１７２０ｃｍ－１ピーク吸光度／２９３０ｃｍ－１ピーク吸光度）が０．０５以上である酸化ポリエチレンワックスを含む。
１７２０ｃｍ－１のピークは、ポリエチレンワックスの酸化が進むと現れるピークであり、２９３０ｃｍ－１ピークは、ポリエチレンワックスを示す炭化水素結合のピークである。酸化ポリエチレンワックスとしてこれらのピークの比が０．０５以上、すなわち、一定以上酸化が進んだポリエチレンワックスを使用することで、成形品の表面不良の低減効果を発揮することができる。 [Oxidized polyethylene wax]
Chlorine-containing resin composition of the present invention, the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement (1720 cm -1 peak absorbance / 2930 cm -1 peak absorbance) is 0.05 or more It contains some oxidized polyethylene wax.
The peak at 1720 cm -1 is a peak that appears as the oxidation of polyethylene wax proceeds, and the peak at 2930 cm -1 is a peak of hydrocarbon bonds indicating polyethylene wax. By using polyethylene wax in which the ratio of these peaks is 0.05 or more, that is, oxidation progresses more than a certain level as oxidized polyethylene wax, it is possible to exert the effect of reducing surface defects of a molded article.
酸化ポリエチレンワックスは、酸価が１ｍｇＫＯＨ／ｇ以上であることが好ましい。酸価が１ｍｇＫＯＨ／ｇ以上であると、樹脂との相溶性が向上し成形品の外観不良を抑制する効果がより充分に発揮される。酸化ポリエチレンワックスの酸価はより好ましくは、５ｍｇＫＯＨ／ｇ以上であり、更に好ましくは、１０ｍｇＫＯＨ／ｇ以上である。また、３０ｍｇＫＯＨ／ｇ以下であることが好ましい。 The oxidized polyethylene wax preferably has an acid value of 1 mg KOH / g or more. When the acid value is 1 mg KOH / g or more, the compatibility with the resin is improved, and the effect of suppressing the appearance defect of the molded product is more sufficiently exhibited. The acid value of the oxidized polyethylene wax is more preferably 5 mg KOH / g or more, still more preferably 10 mg KOH / g or more. Moreover, it is preferable that it is 30 mgKOH / g or less.
酸化ポリエチレンワックスは、密度が１．００ｇ／ｃｍ３以下であることが好ましい。密度が１．００ｇ／ｃｍ３以下であると、樹脂の溶融粘度が下がり、より成形性が向上する。酸化ポリエチレンワックスの密度はより好ましくは、０．９５ｇ／ｃｍ３以下である。 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 moldability is further improved. The density of the oxidized polyethylene wax is more preferably 0.95 g / cm 3 or less.
酸化ポリエチレンワックスは、融点が８０℃以上であることが好ましい。融点が８０℃以上であると、昇華物等が減少し、本発明の塩素含有樹脂組成物が成形加工性において成形品の表面不良の低減効果を発揮することができる。酸化ポリエチレンワックスの融点は、より好ましくは、８５℃以上であり、更に好ましくは、９０℃以上である。また、酸化ポリエチレンワックスの融点は、通常、１５０℃以下である。 The oxidized polyethylene wax preferably has a melting point of 80 ° C. or higher. When the melting point is 80 ° C. or more, the sublimate and the like decrease, and the chlorine-containing resin composition of the present invention can exhibit the effect of reducing the surface defects of the molded product in the molding processability. The melting point of the oxidized polyethylene wax is more preferably 85 ° C. or more, still more preferably 90 ° C. or more. The melting point of the oxidized polyethylene wax is usually 150 ° C. or less.
酸化ポリエチレンワックスは、１４０℃での粘度が１０００ｃｐｓ以下であることが好ましい。１４０℃での粘度が１０００ｃｐｓ以下であると、本発明の塩素含有樹脂組成物が成形加工性に優れたものとなる。酸化ポリエチレンワックスの１４０℃での粘度は、８００ｃｐｓ以下であることが好ましい。より好ましくは、５００ｃｐｓ以下である。 The oxidized polyethylene wax preferably has a viscosity of 1,000 cps or less at 140.degree. When the viscosity at 140 ° C. is 1000 cps or less, the chlorine-containing resin composition of the present invention is excellent in molding processability. The viscosity at 140 ° C. of the oxidized polyethylene wax is preferably 800 cps or less. More preferably, it is 500 cps or less.
本明細書中、酸化ポリエチレンワックスの酸価、密度、融点及び１４０℃での粘度は全て実施例に記載の方法で測定する。 In the present specification, the acid value, density, melting point and viscosity at 140 ° C. of the oxidized polyethylene wax are all measured by the methods described in the examples.
酸化ポリエチレンワックスとしては、例えば、三井化学社製ハイワックスシリーズ、三洋化成工業社製サンワックスシリーズ、三洋化成工業社製ビスコールシリーズ、日本精蝋社製ルバックスシリーズ、ハニウェル社製ＡＣシリーズ等が挙げられ、そのうち、上記物性を満たすものを適宜用いることができる。 As polyethylene oxide wax, for example, high wax series made by Mitsui Chemicals, Sanwax series made by Sanyo Chemical Industries, Viscor series made by Sanyo Chemical Industries, Luvacs series made by Nippon Seiwa Co., AC series made by Honeywell, etc. Among them, those which satisfy the above-mentioned physical properties can be appropriately used.
本発明の塩素含有樹脂組成物における酸化ポリエチレンワックスの含有量は、塩素含有樹脂１００質量部に対し、０．０１～２．０質量部であることが好ましい。これにより、成形品の外観不良を抑制する効果がより充分に発揮される。より好ましくは０．０１～１．５質量部であり、更に好ましくは０．０１～１．０質量部である。 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 with respect to 100 parts by mass of the chlorine-containing resin. Thereby, the effect which suppresses the appearance defect of a molded article is exhibited more fully. More preferably, it is 0.01 to 1.5 parts by mass, and still more preferably 0.01 to 1.0 parts by mass.
［ハイドロタルサイト］
本発明の塩素含有樹脂組成物に含まれるハイドロタルサイトは特に制限されないが、マグネシウム元素（Ｍｇ）及び／又は亜鉛元素（Ｚｎ）と、アルミニウム元素（Ａｌ）とを含むものが好ましい。 [Hydrotalcite]
The hydrotalcite contained in the chlorine-containing resin composition of the present invention is not particularly limited, but one containing magnesium element (Mg) and / or zinc element (Zn) and aluminum element (Al) is preferable.
上記ハイドロタルサイト型粉体として特に好ましくは、下記一般式（１）：
｛（Ｍｇ）ｘ（Ｚｎ）ｙ｝（Ａｌ）ｚ（ＯＨ）２（Ａｎ－）ｘ／ｎ・ｍＨ２Ｏ  （１）
（式中、Ａｎ－は、ｎ価の層間アニオンを表す。ｘ、ｙ及びｚは、０＜ｘ＜１、０≦ｙ＜１、０．２≦ｚ≦０．４、ｘ＋ｙ＋ｚ＝１を満たす数であって、かつｘ＋ｙとｚとの比｛（ｘ＋ｙ）／ｚ｝は２．２以下である。ｎ及びｍは、それぞれ１≦ｎ≦４、及び、０≦ｍを満たす数である。）で表されるものである。これにより、塩素含有樹脂組成物の耐熱性や熱安定性がより向上する。 Particularly preferably as the above hydrotalcite type powder, the following general formula (1):
{(Mg) x (Zn) y} (Al) z (OH) 2 (A n-) x / n · mH 2 O (1)
(In the formula, A n− represents an n-valent interlayer anion. X, y and z represent 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, x + y + z = 1 And the ratio of {x + y) / z} of x + y to z is 2.2 or less, and n and m are numbers satisfying 1 ≦ n ≦ 4 and 0 ≦ m, respectively. It is represented by.). Thereby, the heat resistance and thermal stability of the chlorine-containing resin composition are further improved.
上記一般式（１）中、ｎ価の層間アニオンとしては特に限定されないが、反応性及び環境負荷低減の観点から、水酸化物イオン（ＯＨ－）、炭酸イオン（ＣＯ３ ２－）及び硫酸イオン（ＳＯ４ ２－）からなる群より選択される少なくとも１種が好適である。中でも、炭酸イオンが好ましい。 In the general formula (1) it is not particularly restricted but includes n-valent interlayer anion, in view of reactivity and environmental load reduction, the hydroxide ion (OH -), carbonate ions (CO 3 2-) and sulfate ions At least one selected from the group consisting of (SO 4 2- ) is preferred. Among them, carbonate ion is preferable.
ｘ、ｙ及びｚは、０＜ｘ＜１、０≦ｙ＜１、０．２≦ｚ≦０．４、ｘ＋ｙ＋ｚ＝１を満たす数であって、かつｘ＋ｙとｚとの比｛（ｘ＋ｙ）／ｚ｝は２．２以下である。
ここで、ｙ＝０であるものは、Ｍｇ／Ａｌ系ハイドロタルサイトと称され、０＜ｙであるものは、亜鉛変性ハイドロタルサイトと称される。本発明では、これらのいずれも好適に使用できる。 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, what is y = 0 is called Mg / Al type hydrotalcite, and what is 0 <y is called zinc modified hydrotalcite. In the present invention, any of these can be suitably used.
ｘ＋ｙとｚとの比｛（ｘ＋ｙ）／ｚ｝は、好ましくは２．１以下、より好ましくは２．０５以下である。下限は特には限定されないが１．９以上が好ましく、より好ましくは２．０以上である。 The ratio {(x + y) / z} of x + y to 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は、１≦ｎ≦４を満たす数であり、層間アニオンの価数によって適宜調整すればよい。 n is a number satisfying 1 ≦ n ≦ 4, and may be appropriately adjusted according to the valence of the interlayer anion.
ハイドロタルサイトは、吸油量が５０ｍｌ／１００ｇ以下であることが好ましい。これにより、本発明の塩素含有樹脂組成物から得られる成形品の光沢が向上する。ハイドロタルサイトの吸油量は、より好ましくは、４５ｍｌ／１００ｇ以下であり、更に好ましくは４０ｍｌ／１００ｇ以下である。また、耐熱性の観点から５ｍｌ／１００ｇ以上であることが好ましい。より好ましくは１０ｍｌ／１００ｇ以上である。 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 hydrotalcite is more preferably 45 ml / 100 g or less, still more preferably 40 ml / 100 g or less. Moreover, it is preferable that it is 5 ml / 100 g or more from a heat resistant viewpoint. More preferably, it is 10 ml / 100 g or more.
本明細書中、ハイドロタルサイト型粉体の吸油量は、ＪＩＳ Ｋ５１０１－１３－１（２００４年：精製あまに油法）に準拠して測定する。 In the present specification, the oil absorption of the hydrotalcite-type powder is measured in accordance with JIS K5101-13-1 (2004: refined linseed oil method).
上記ハイドロタルサイトの粒子の形状は特に限定されず、例えば、板状、球状、円盤状等が挙げられる。中でも、板又は円盤状であることが好ましい。
なお、粒子形状は、走査型電子顕微鏡等によって観察することができる。 The shape of the particles of the hydrotalcite is not particularly limited, and examples thereof include plate, sphere, and disc. Among them, a plate or a disc is preferable.
The particle shape can be observed by a scanning electron microscope or the like.
上記ハイドロタルサイト粒子の平均粒子径は、例えば、０．１μｍ以上、２．０μｍ以下であることが好ましい。これにより、塩素含有樹脂への分散性が向上し、本発明の作用効果がより向上する。より好ましくは０．３μｍ以上であり、また、より好ましくは１．５μｍ以下である。 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 to chlorine containing resin improves and the effect of this invention improves more. More preferably, it is 0.3 μm or more, and more preferably, 1.5 μm or less.
本明細書中、平均粒子径は、例えば、レーザー回折粒度分布測定装置（ＨＯＲＩＢＡ製ＬＡ９５０）を用いてＤ５０として測定することができる。
Ｄ５０とは、体積基準での５０％積算粒径を意味する。 In the present specification, the average particle size can be measured as D50 using, for example, a laser diffraction particle size distribution measuring apparatus (LA950 manufactured by HORIBA).
D50 means 50% cumulative particle size on a volume basis.
上記ハイドロタルサイトの比表面積（ＳＳＡとも称す）は、例えば、１ｍ２／ｇ以上、５０ｍ２／ｇ以下であることが好ましい。これにより、塩素含有樹脂への分散性が向上し、本発明の作用効果がより向上する。より好ましくは５ｍ２／ｇ以上、更に好ましくは１０ｍ２／ｇ以上であり、また、より好ましくは４０ｍ２／ｇ以下、更に好ましくは３０ｍ２／ｇ以下である。
比表面積がこの範囲であると、耐熱性に優れた樹脂組成物を得ることが出来る。 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 to chlorine containing resin improves and the effect of this invention improves more. More preferably, it is 5 m 2 / g or more, further preferably 10 m 2 / g or more, and more preferably 40 m 2 / g or less, more preferably 30 m 2 / g or less.
The resin composition excellent in heat resistance can be obtained as a specific surface area is this range.
本明細書中、比表面積は、ＢＥＴ法により得られたＢＥＴ比表面積（ＳＳＡとも称す）を意味する。ＢＥＴ法は、窒素等の気体粒子を固体粒子に吸着させ、吸着した量から比表面積を測定する気体吸着法であり、圧力Ｐと吸着量Ｖとの関係からＢＥＴ式によって単分子吸着量ＶＭを求めることで、比表面積が定まる。
具体的には、以下の条件によりＢＥＴ比表面積を測定する。 In the present 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 from the amount adsorbed. From the relationship between pressure P and adsorption amount V, the monomolecular adsorption amount VM is calculated by the BET equation. The specific surface area is determined by finding it.
Specifically, the BET specific surface area is measured under the following conditions.
〔比表面積の測定条件〕
使用機：マウンテック社製、Ｍａｃｓｏｒｂ　Ｍｏｄｅｌ　ＨＭ－１２２０
吸着ガス：窒素（Ｎ２）
外部脱気装置の脱気条件：１０５℃－１５分
比表面積測定装置本体の脱気条件：１０５℃－５分 [Measurement conditions of specific surface area]
Machine used: Mounttech Inc., Macsorb Model HM-1220
Adsorbed gas: nitrogen (N 2 )
Degassing condition of external degassing device: 105 ° C-15 minutes Specific surface area measuring device degassing condition: 105 ° C-5 minutes
上記ハイドロタルサイトは、粉体中の粒子が被覆層を有していてもよい。この場合、当該被覆層を有する粒子を含むハイドロタルサイトの物性が、上記物性（粒子形状、平均粒子径、比表面積等）を満たすことが好ましい。被覆層としては特に限定されないが、表面処理剤を用いて表面処理を行って被覆したものであることが好ましい。 In the above hydrotalcite, the particles in the powder may have a coating layer. In this case, it is preferable that the physical properties of the hydrotalcite containing the particles having the coating layer satisfy the above-mentioned physical properties (particle shape, average particle size, specific surface area, etc.). Although it does not specifically limit as a coating layer, It is preferable that it surface-treats and coats using a surface treating agent.
上記表面処理剤としては特に限定されず、例えば、高級脂肪酸、高級脂肪酸金属塩（金属石ケン）、アニオン界面活性剤、リン酸エステル、シランカップリング剤、チタンカップリング剤、アルミニウムカップリング剤等のカップリング剤が挙げられる。なお、１種又は２種以上を使用することができる。 The surface treatment agent is not particularly limited, and, for example, higher fatty acids, higher fatty acid metal salts (metal soaps), anionic surfactants, phosphoric esters, silane coupling agents, titanium coupling agents, aluminum coupling agents, etc. Coupling agents are mentioned. In addition, 1 type or 2 types or more can be used.
より具体的な表面処理剤としては、例えば、ステアリン酸、オレイン酸、エルカ酸、パルミチン酸、ラウリン酸等の高級脂肪酸、これら高級脂肪酸のリチウム塩、ナトリウム塩、カリウム塩等の金属塩；ステアリルアルコール、オレイルアルコール等の高級アルコールの硫酸エステル塩、ポリエチレングリコールエーテルの硫酸エステル塩、アミド結合硫酸エステル塩、エーテル結合スルホン酸塩；エステル結合スルホネート、アミド結合アルキルアリールスルホン酸塩、エーテル結合アルキルアリールスルホン酸塩等のアニオン界面活性剤；オルトリン酸とオレイルアルコール、ステアリルアルコール等とのモノ又はジエステル又はこれらの混合物であって、それらの酸型又はアルカリ金属塩又はアミン塩等のリン酸エステル；ビニルエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、γ－アミノプロピルトリメトキシシラン等のシランカップリング剤；イソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリデシルベンゼンスルホニルチタネート等のチタンカップリング剤；アセトアルコキシアルミニウムジイソプロピレート等のアルカリカップリング剤；を挙げることができる。 More specific surface treatment agents are, for example, higher fatty acids such as stearic acid, oleic acid, erucic acid, palmitic acid and lauric acid, metal salts such as lithium salts, sodium salts and potassium salts of these higher fatty acids; stearyl alcohol , Sulfuric acid ester salts of higher alcohols such as oleyl alcohol, sulfuric acid ester salts of polyethylene glycol ether, amide bond sulfuric acid ester salts, ether bond sulfonates; ester bond sulfonates, amide bond alkyl aryl sulfonates, ether bond alkyl aryl sulfonic acid Anionic surfactants such as salts; mono- or diesters of orthophosphoric acid with oleyl alcohol, stearyl alcohol etc. or mixtures thereof, phosphates such as acid type or alkali metal salts or amine salts thereof; Silane, γ-methacryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, silane coupling agents such as γ-aminopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl Examples include titanium coupling agents such as tridecyl benzene sulfonyl titanate; and alkaline coupling agents such as acetoalkoxyaluminum diisopropylate.
上記表面処理剤の使用量は特に限定されないが、例えば、最終的に得られる被覆層を有する粒子を含むハイドロタルサイト１００質量％に対し、表面処理剤による被覆量が０．１～３０質量％の範囲となるように表面処理剤の使用量を調節することが好ましい。より好ましくは０．１～２０質量％の範囲である。 The amount of the surface treatment agent to be used is not particularly limited. For example, the amount of the surface treatment agent coated is 0.1 to 30% by mass with respect to 100% by mass of hydrotalcite containing particles having a finally obtained coated layer. It is preferable to adjust the amount of the surface treatment agent to be in the range of More preferably, it is in the range of 0.1 to 20% by mass.
上記樹脂組成物において、ハイドロタルサイトの含有量は、例えば、塩素含有樹脂１００質量部に対し、０．０５質量部以上であることが好ましく、また、１０質量部以下であることが好ましい。これにより、耐熱性及び熱安定性が更に向上する。より好ましくは０．１質量部以上、また、より好ましくは８質量部以下、更に好ましくは５質量部以下である。 In the resin composition, the content of the hydrotalcite is, for example, preferably 0.05 parts by mass or more, and preferably 10 parts by mass or less with respect to 100 parts by mass of the chlorine-containing resin. This further improves the heat resistance and the heat stability. More preferably, it is 0.1 parts by mass or more, more preferably 8 parts by mass or less, and still more preferably 5 parts by mass or less.
［β－ジケトン化合物、β－ジケト金属塩］
本発明の塩素含有樹脂組成物はまた、β－ジケトン化合物及び／又はβ－ジケト金属塩を含むことで、成形時の着色性改善を図ることができる。 [Β-diketone compounds, β-diketo metal salts]
The chlorine-containing resin composition of the present invention can also improve the colorability at the time of molding by containing the β-diketone compound and / or the β-diketo metal salt.
β－ジケトン化合物としては特に限定されないが、例えば、アセチルアセトンや、ステアロイルアセチルメタン、ベンゾイルアセチルメタン、ジベンゾイルメタン、ステアロイルベンゾイルメタン、オクチルベンゾイルメタン、ビス（４－オクチルベンゾイル）メタン、４－メトキシベンゾイルベンゾイルメタン、ビス（４－カルボキシメチルベンゾイル）メタン、２－カルボキシメチルベンゾイルアセチルオクチルメタン、２－ベンゾイルシクロヘキサン等のアルカノイルアロイルメタンやジアロイルメタンが好適である。
β－ジケト金属塩としては、上記β－ジケトン化合物の金属塩が好適である。金属塩の金属種としては特に限定されないが、例えば、カルシウムや亜鉛等が挙げられる。 The β-diketone compound is not particularly limited. For example, acetylacetone, stearoylacetylmethane, benzoylacetylmethane, dibenzoylmethane, stearoylbenzoylmethane, octylbenzoylmethane, bis (4-octylbenzoyl) methane, 4-methoxybenzoylbenzoylone. Alkanoylaroylmethane such as methane, bis (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, 2-benzoylcyclohexane and the like and diaroylmethane are preferred.
As the β-diketo metal salt, metal salts of the above-mentioned β-diketone compounds are preferable. The metal species of the metal salt is not particularly limited, and examples thereof include calcium and zinc.
上記樹脂組成物におけるβ－ジケトン化合物及び／又はβ－ジケト金属塩の含有量は、塩素含有樹脂１００質量部に対して２．０質量部以下であることが好ましい。より好ましくは０．０１～１．０質量部である。 The content of the β-diketone compound and / or the β-diketo metal salt in the above 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 to 1.0 parts by mass.
［離型剤］
本発明の塩素含有樹脂組成物はまた、離型剤を含むことが好ましい。離型剤としては、ジペンタエリスリトールヘキサステアレート、ペンタエリスリトールテトラステアレート等が挙げられるが、これらの中でもジペンタエリスリトールヘキサステアレートを含むことが好ましい。これにより、本発明の塩素含有樹脂組成物のかすれや筋引きの発生をより充分に抑制することができる。 [Release agent]
The chlorine-containing resin composition of the present invention preferably also contains a release agent. Examples of the mold release agent include dipentaerythritol hexastearate and pentaerythritol tetrastearate. Among these, it is preferable to include dipentaerythritol hexastearate. This makes it possible to more sufficiently suppress the occurrence of lightening and streaking of the chlorine-containing resin composition of the present invention.
本発明の塩素含有樹脂組成物が離型剤を含む場合、その含有量は特に限定されず、例えば、塩素含有樹脂１００質量部に対して０．０１～５．０質量部であることが好ましい。より好ましくは、０．０１～２．０質量部である。 When the chlorine-containing resin composition of the present invention contains a mold release agent, the content thereof is not particularly limited. For example, the content is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the chlorine-containing resin . More preferably, it is 0.01 to 2.0 parts by mass.
［充填剤］
本発明の塩素含有樹脂組成物はまた、充填剤を含むことが好ましい。これにより、成形品の寸法安定性や成形品の強度が向上するので、成形体用途に好ましい樹脂組成物となる。充填剤は中和剤としても機能する。 [filler]
The chlorine-containing resin composition of the present invention preferably also contains a filler. As a result, the dimensional stability of the molded product and the strength of the molded product are improved, so that the resin composition is preferable for molded product applications. The filler also functions as a neutralizing agent.
充填剤としては特に限定されず、無機塩類、無機酸化物、無機水酸化物等の無機粉体が挙げられ、例えば、亜鉛、チタン、鉄、セリウム、バリウム、カルシウム、ケイ素、アルミニウム、マグネシウム、ストロンチウム、硼素、ジルコニウム等の塩類、酸化物、水酸化物、複合酸化物が挙げられる。塩類としては特に限定されず、例えば、硫酸塩、炭酸塩、塩化塩、酢酸塩、硝酸塩等が挙げられる。具体的には、例えば、炭酸カルシウム、炭酸亜鉛、炭酸マグネシウム、シリカ、酸化亜鉛、酸化チタン、酸化セリウム、酸化鉄、硫酸バリウム、硫酸ストロンチウム、硫酸マグネシウム、酸化ケイ素、酸化アルミニウム、酸化マグネシウム、ケイ酸亜鉛、チタン酸亜鉛、チタン酸バリウム、タルク等が挙げられ、中でも、炭酸カルシウムが好適である。 The filler is not particularly limited, and examples thereof include inorganic powders such as inorganic salts, inorganic oxides and inorganic hydroxides, and examples thereof include zinc, titanium, iron, cerium, barium, calcium, silicon, aluminum, magnesium, strontium And salts such as boron and zirconium, oxides, hydroxides and complex oxides. The salts are not particularly limited, and examples thereof include sulfates, carbonates, chlorides, acetates and nitrates. Specifically, for example, calcium carbonate, zinc carbonate, magnesium carbonate, silica, zinc oxide, titanium oxide, cerium oxide, cerium oxide, iron oxide, barium sulfate, strontium sulfate, magnesium sulfate, silicon oxide, aluminum oxide, magnesium oxide, silicic acid Zinc, zinc titanate, barium titanate, talc and the like can be mentioned, among which calcium carbonate is preferred.
炭酸カルシウムの中でも、比表面積（ＢＥＴ比表面積）が２５ｍ２／ｇ未満であるものが好ましい。より好ましくは２３ｍ２／ｇ以下、更に好ましくは２０ｍ２／ｇ以下、特に好ましくは１８ｍ２／ｇ以下であり、また、下限は０．１ｍ２／ｇ以上が好ましい。より好ましくは０．５ｍ２／ｇ以上である。上記範囲を超える場合には、加工時にプレートアウトを生じる等の悪影響を与えるおそれがある。 Among calcium carbonates, one having a specific surface area (BET specific surface area) of less than 25 m 2 / g is preferable. More preferably, it is 23 m 2 / g or less, 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. If the above range is exceeded, there is a possibility that adverse effects such as plate out may occur during processing.
上記樹脂組成物が充填剤を含む場合、その含有量は特に限定されず、例えば、塩素含有樹脂１００質量部に対して４０質量部以下であることが好ましい。４０質量部を超えるとプレートアウトが抑制されないことがある。より好ましくは３０質量部以下、更に好ましくは１～３０質量部である。より更に好ましくは２５質量部以下、一層更に好ましくは２０質量部以下、特に好ましくは１０質量部以下であり、また下限は１質量部以上が好ましく、より好ましくは２質量部以上、更に好ましくは３質量部以上である。最も好ましくは、比表面積が２０ｍ２／ｇ以下である炭酸カルシウムの含有量がこれらの好ましい範囲内にあることである。 When the said resin composition contains a filler, the 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 resin. If it exceeds 40 parts by mass, plate out may not be suppressed. The amount is more preferably 30 parts by mass or less, still more preferably 1 to 30 parts by mass. Still 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, still more preferably 3 It is more than mass part. Most preferably, the content of calcium carbonate having a specific surface area of 20 m 2 / g or less is within these preferable ranges.
［その他の成分］
本発明の塩素含有樹脂組成物は更に、必要に応じてその他の成分を含んでもよい。例えば、耐熱助剤、上記（ｃ）の酸化ポリエチレンワックス以外の滑剤、紫外線吸収剤、酸化防止剤、架橋助剤、可塑剤等の各種添加剤が挙げられる。添加剤はそれぞれ特に限定されないが、例えば、耐熱助剤としてはジペンタリスリトール等の多価アルコール化合物や、エポキシ樹脂等のエポキシ化合物が挙げられ、滑剤としてはステアリン酸モノグリセライド、パルミチン酸モノグリセライド、ステアリン酸、パルミチン酸、上記（ｃ）の酸化ポリエチレンワックス以外のポリエチレンワックス等が挙げられ、紫外線吸収剤としてはベンゾフェノン系化合物、ベンゾトリアゾール系化合物、芳香族ベンゾエート系化合物等が挙げられ、酸化防止剤としてはフェノール系化合物等が挙げられ、架橋助剤としてはトリメチロールプロパントリメタクリレート、ジペンタエリスリトールヘキサアクリレート等が挙げられ、可塑剤としてはジオクチルフタレート（ＤＯＰ）やトリオクチルトリメリテート（ＴＯＴＭ）、ジオクチルアジペート（ＤＯＡ）等が挙げられる。 [Other ingredients]
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 light absorber, an antioxidant, a crosslinking auxiliary agent, a plasticizer and the like can be mentioned. The additives are not particularly limited, but examples thereof include polyhydric alcohol compounds such as dipentalithitol and epoxy compounds such as epoxy resin as a heat-resistant assistant, and monoglycerides of stearic acid, monoglycerides of palmitic acid and stearin as lubricants. Acid, palmitic acid, polyethylene wax other than the oxidized polyethylene wax of (c) mentioned above, etc., UV absorbers include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds etc., and as antioxidants Examples of the crosslinking aid include trimethylolpropane trimethacrylate and dipentaerythritol hexaacrylate. Examples of the plasticizer include dioctyl phthalate (DOP) and trioctyl trimellime. Over preparative (TOTM), dioctyl adipate (DOA), and the like.
本発明の塩素含有樹脂組成物は、組成物全体に対する可塑剤の含有量が５重量％以下であることが好ましい。外観不良が生じやすいのは可塑剤の含有量が少ない硬質系の樹脂組成物から得られた成形品の場合である。したがって、樹脂組成物が可塑剤の含有量が少ない硬質系のものである場合に、本発明の効果がより顕著に発揮されることになる。可塑剤の含有量は、より好ましくは、１．０重量％以下であり、更に好ましくは、０．０１重量％以下である。 The chlorine-containing resin composition of the present invention preferably has a plasticizer content of 5% by weight or less based on the entire composition. Defective appearance is apt to occur in the case of a molded product obtained from a hard resin composition having a small content of plasticizer. Therefore, when the resin composition is a hard type having a small content of a plasticizer, the effects of the present invention will be more significantly exhibited. The content of the plasticizer is more preferably 1.0% by weight or less, still more preferably 0.01% by weight or less.
本発明を詳細に説明するために以下に実施例を挙げるが、本発明はこれらの実施例のみに限定されるものではない。 The following examples are provided to describe the present invention in detail, but the present invention is not limited to these examples.
１．原料
後述の表１－１、表１－２に記載する原料は以下のとおりである。
（ａ）塩素含有樹脂
塩化ビニル系樹脂：信越化学工業社製、ＴＫ－１０００、重合度１０００ 1. Raw Materials Raw materials listed in Tables 1-1 and 1-2 described later are as follows.
(A) Chlorine-containing resin: Vinyl chloride resin: Shin-Etsu Chemical Co., Ltd., TK-1000, degree of polymerization: 1000
（ｂ）有機酸亜鉛
ステアリン酸亜鉛：堺化学工業社製、ＳＺ－Ｐ（Ｃａ－Ｚｎ系安定剤） (B) Organic acid zinc stearate: SZ-P (Ca-Zn stabilizer) manufactured by Sakai Chemical Industry Co., Ltd.
（ｃ）酸化ポリエチレンワックス
ＡＣポリエチレン６２９Ａ：ハニウェル社製
ＡＣポリエチレン６５６：ハニウェル社製
ＡＣポリエチレン３０７Ａ：ハニウェル社製
ＡＣポリエチレン３１６Ａ：ハニウェル社製
ＡＣポリエチレン６Ａ：ハニウェル社製 (C) Oxidized polyethylene wax AC polyethylene 629A: Honeywell AC polyethylene 656: Honeywell AC polyethylene 307A: Honeywell AC polyethylene 316A: Honeywell AC Polyethylene 6A: Honeywell
（ｄ）ハイドロタルサイト
特許第５０５６０１４号公報の実施例４に記載のハイドロタルサイトの製造操作にて、硫酸マグネシウム、硫酸アルミニウム及び硫酸亜鉛の各モル比、並びに、製造条件を種々変化させ合成を行い、製造毎に後述する方法で吸油量と比表面積を測定し、表１－１、表１－２に記載のハイドロタルサイト型粉末を選び出した。 (D) In the hydrotalcite production operation described in Example 4 of Hydrotalcite Patent No. 5056014, each molar ratio of magnesium sulfate, aluminum sulfate and zinc sulfate, and production conditions are changed, and synthesis is performed. The oil absorption and the specific surface area were measured by the method described later for each production, and hydrotalcite-type powders listed in Tables 1-1 and 1-2 were selected.
（ｅ）β－ジケトン化合物、β－ジケト金属塩
ジベンゾイルメタン：ロディア社製、ロディアスタブ８３Ｐ (E) β-diketone compound, β-diketo metal salt dibenzoylmethane: manufactured by Rhodia, Rhodia Stub 83P
（ｆ）充填剤
炭酸カルシウム：株式会社カルファイン製　ＫＳ－１０００、比表面積１．１５ｍ２／ｇ (F) Filler calcium carbonate: Calfine Co., Ltd. KS-1000, specific surface area 1.15 m 2 / g
（ｇ）その他の成分
ステアリン酸カルシウム：堺化学工業社製、ＳＣ－Ｐ（Ｃａ－Ｚｎ系安定剤）
ジペンタエリスリトール：広栄化学社製、ジペンタリット３００
ポリエチレンワックス：三井化学社製、ハイワックス２２０ＭＰ
エステルワックス（ジペンタエリスリトールヘキサステアレート）：理研ビタミン社製、リケスターＳＬ－０２ (G) Other ingredients calcium stearate: manufactured by Sakai Chemical Industry Co., Ltd., SC-P (Ca-Zn stabilizer)
Dipentaerythritol: manufactured by Guangei Chemical, dipentarit 300
Polyethylene wax: made by Mitsui Chemicals, High Wax 220MP
Ester wax (dipentaerythritol hexastearate): RIKEN VITAMINS CO., LTD.
実施例１～８、比較例１～７
実施例、比較例で使用した酸化ポリエチレンワックス、ハイドロタルサイトの物性、及び、それらの酸化ポリエチレンワックスやハイドロタルサイトを含んで調製した樹脂組成物の各成分の配合を表１－１、表１－２に示した。酸化ポリエチレンワックス、ハイドロタルサイトの物性は、以下の測定方法により測定した。
また表１－１、表１－２には、得られた樹脂組成物について、以下の方法により評価した成形品表面の筋引き及び光沢性の評価結果も示した。 Examples 1 to 8 and Comparative Examples 1 to 7
Physical properties of the oxidized polyethylene wax and hydrotalcite used in the examples and comparative examples, and the composition of each component of the resin composition prepared by containing the oxidized polyethylene wax and the hydrotalcite are shown in Table 1-1, Table 1 -2 shown. Physical properties of oxidized polyethylene wax and hydrotalcite were measured by the following measuring methods.
Further, in Table 1-1 and Table 1-2, evaluation results of streaking and gloss of the surface of a molded product, which were evaluated by the following method, of the obtained resin composition are also shown.
＜酸化ポリエチレンワックスの物性測定＞
［酸価］
ＡＳＴＭ　Ｄ－１３８６に準拠して測定した。
［密度］
ＡＳＴＭ　Ｄ－１５０５に準拠して測定した。
［融点（滴点）］
ＡＳＴＭ　Ｄ－３９５４に準拠して測定した。
［１４０℃での粘度］
Ｂ型粘度計（ブルックフィールド社製）により、１４０℃における粘度を測定した。
［ＦＴ－ＩＲピーク強度比］
フーリエ変換赤外分光法により、以下の装置、及び測定方法で測定した。
メーカー名：Ｔｈｅｒｍｏ　Ｆｉｓｈｅｒ　Ｓｃｉｅｎｔｉｆｉｃ
型式：ＮＩＣＯＬＥＴ　４７００
測定方法：ＡＴＲ法／１回反射（使用プレート：ダイアモンドプリズムプレート）
測定手順：
（１）プレートに何も乗せずにバックグラウンドを測定する
（２）バックグラウンド測定後、プレートにサンプルを小さじ１杯程度押し付けて測定する。
（３）試料測定後、『アドバンストＡＴＲ補正』を行い、これを測定結果とする。
＜ハイドロタルサイトの物性測定＞
［吸油量］
ＪＩＳ Ｋ５１０１－１３－１（２００４年：精製あまに油法）に準拠して測定した。 <Measurement of physical properties of oxidized polyethylene wax>
[Acid number]
It was measured in accordance with ASTM D-1386.
[density]
It was measured in accordance with ASTM D-1505.
[Melting point (dropping point)]
It was measured in accordance with ASTM D-3954.
[Viscosity at 140 ° C]
The viscosity at 140 ° C. was measured by a B-type viscometer (manufactured by Brookfield).
[FT-IR peak intensity ratio]
It measured by the following apparatus and measurement method by Fourier-transform infrared spectroscopy.
Manufacturer: Thermo Fisher Scientific
Model: NICOLET 4700
Measurement method: ATR method / single reflection (use plate: diamond prism plate)
Measurement procedure:
(1) Measure the background without putting anything on the plate (2) After the background measurement, press the sample about a teaspoon on the plate and 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]
It was measured in accordance with JIS K5101-13-1 (2004: refined linseed oil method).
＜成形加工＞
冷却機能を備えた吸引サイジング（成形品の表面性を平滑にする装置）を有するラボ押出機（東洋精機社製、コニカル２Ｄ２０Ｃ型）にて上記樹脂組成物を使用し、５時間連続してパイプを押出成形し、一定の長さ毎に切断して、パイプ成形品を得た。
押出条件は、以下のように設定した。シリンダー温度は、原料投入口から近い位置から、シリンダー温度１：１７５℃、シリンダー温度２：１８０℃、シリンダー温度３：１８５℃とし、アダプター金型温度を１８５℃、金型１を１８０℃、金型２を２０５℃とした。金型はパイプ用を使用した。 <Molding process>
Using the above resin composition in a laboratory extruder (conical 2D20C manufactured by Toyo Seiki Co., Ltd.) having suction sizing (a device for smoothing the surface properties of molded articles) having a cooling function, the pipe is continuously used for 5 hours Was extruded and cut into fixed lengths to obtain a pipe molded product.
The extrusion conditions were set as follows. The cylinder temperature is from the position close to the raw material inlet, cylinder temperature 1: 175 ° C, cylinder temperature 2: 180 ° C, cylinder temperature 3: 185 ° C, adapter mold temperature 185 ° C, mold 1 180 ° C, gold The mold 2 was at 205 ° C. The mold used was for pipes.
＜樹脂組成物の評価＞
［筋引き］
押出成形開始から所定の時間経過後に得られたパイプ成形品の筋引き発生状況（すなわち、パイプ成形品のキズの発生状況）を目視にて確認し、以下の基準で評価した。
◎：５時間後の成形されたパイプ成形品にキズは確認されなかった。
〇：３時間後の成形されたパイプ成形品にキズが確認された。
△：１時間後の成形されたパイプ成形品にキズが確認された。
×：１時間以内に成形されたパイプ成形品にキズが確認された。
［光沢性］
押出成形開始から所定の時間経過後に得られたパイプ成形品の光沢性の状況を目視にて確認し、以下の基準で評価した。
◎：５時間後の成形されたパイプ成形品に光沢が保たれていることが確認された。
〇：３時間後は光沢が確認されたが、５時間後の成形されたパイプ成形品には光沢が無く、成形パイプの表面がかすれた状態になっているのが確認された。
△：１時間後は光沢が確認されたが、３時間後の成形されたパイプ成形品には光沢が無く、成形パイプの表面がかすれた状態になっているのが確認された。
×：成形直後から光沢が無く、成形パイプの表面がかすれた状態になっているのが確認された。 <Evaluation of resin composition>
[Muscle pull]
The occurrence of creasing (that is, the occurrence of flaws in the pipe molded article) of the pipe molded article obtained after a predetermined time elapsed from the start of extrusion molding was visually confirmed and evaluated according to the following criteria.
◎: no flaw was observed in the molded pipe after 5 hours.
A: A flaw was found on the molded pipe after 3 hours.
Δ: Scratches were observed on the molded pipe after 1 hour.
X: Scratches were confirmed on the pipe molded product molded within 1 hour.
[Glossy]
The glossiness of the pipe formed 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 molded pipe formed article after 5 hours maintained its gloss.
Good: Gloss was confirmed after 3 hours, but it was confirmed that the molded pipe molded product after 5 hours had no gloss and that the surface of the molded pipe was in a faded state.
Δ: Gloss was confirmed after 1 hour, but it was confirmed that the molded pipe molded product after 3 hours had no gloss and that the surface of the molded pipe was in a faded state.
X: There was no gloss immediately after molding, and it was confirmed that the surface of the molded pipe was in a faded state.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表１－１、表１－２の結果から、ＦＴ－ＩＲ測定における１７２０ｃｍ－１のピークと２９３０ｃｍ－１のピークとの吸光度の比が０．０５以上である酸化ポリエチレンワックスを含むことで、Ｃａ－Ｚｎ系安定剤を使用した塩素含有樹脂組成物の成形品表面の不良の発生を効果的に抑制することができることが確認された。 Table 1-1, the results in Table 1-2, that the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement comprises oxidized polyethylene wax is 0.05 or more, Ca It has been confirmed that the generation of defects on the surface of a molded article of a chlorine-containing resin composition using a Zn-based stabilizer can be effectively suppressed.

Claims (9)

  1. （ａ）塩素含有樹脂、（ｂ）有機酸亜鉛、（ｃ）酸化ポリエチレンワックス、（ｄ）ハイドロタルサイト、並びに、（ｅ）β－ジケトン化合物及び／又はβ－ジケト金属塩を含み、
    該（ｃ）酸化ポリエチレンワックスは、ＦＴ－ＩＲ測定における１７２０ｃｍ－１のピークと２９３０ｃｍ－１のピークとの吸光度の比（１７２０ｃｍ－１ピーク吸光度／２９３０ｃｍ－１ピーク吸光度）が０．０５以上である
    ことを特徴とする塩素含有樹脂組成物。     (A) chlorine-containing resin, (b) zinc organic acid, (c) polyethylene oxide wax, (d) hydrotalcite, and (e) β-diketone compound and / or β-diketo metal salt,
    The (c) oxidized polyethylene wax, the ratio of the absorbance of the peak of the 2930 cm -1 in 1720 cm -1 in the FT-IR measurement (1720 cm -1 peak absorbance / 2930 cm -1 peak absorbance) is 0.05 or more Chlorine containing resin composition characterized by the above-mentioned.
  2. 前記（ｃ）酸化ポリエチレンワックスは、酸価が１ｍｇＫＯＨ／ｇ以上であることを特徴とする請求項１に記載の塩素含有樹脂組成物。 The chlorine-containing resin composition according to claim 1, wherein the (c) oxidized polyethylene wax has an acid value of 1 mg KOH / g or more.
  3. 前記（ｃ）酸化ポリエチレンワックスは、密度が０．９５ｇ／ｃｍ３以下であることを特徴とする請求項１又は２に記載の塩素含有樹脂組成物。 Wherein (c) oxidized polyethylene wax are chlorine-containing resin composition according to claim 1 or 2, wherein the density is 0.95 g / cm 3 or less.
  4. 前記（ｃ）酸化ポリエチレンワックスは、融点が８０℃以上であることを特徴とする請求項１～３のいずれかに記載の塩素含有樹脂組成物。 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.
  5. 前記（ｃ）酸化ポリエチレンワックスは、１４０℃での溶融粘度が１０００ｃｐｓ以下であることを特徴とする請求項１～４のいずれかに記載の塩素含有樹脂組成物。 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 not more than 1000 cps.
  6. 前記（ｄ）ハイドロタルサイトは、吸油量が５０ｍｌ／１００ｇ以下であることを特徴とする請求項１～５のいずれかに記載の塩素含有樹脂組成物。 The chlorine-containing resin composition according to any one of claims 1 to 5, wherein the (d) hydrotalcite has an oil absorption of 50 ml / 100 g or less.
  7. 前記塩素含有樹脂組成物は、更に（ｆ）ジペンタエリスリトールヘキサステアレートを含むことを特徴とする請求項１～６のいずれかに記載の塩素含有樹脂組成物。 The chlorine-containing resin composition according to any one of claims 1 to 6, wherein the chlorine-containing resin composition further comprises (f) dipentaerythritol hexastearate.
  8. 前記塩素含有樹脂組成物は、組成物全体に対する可塑剤の含有量が５重量％以下であることを特徴とする請求項１～７のいずれかに記載の塩素含有樹脂組成物。 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.
  9. 前記塩素含有樹脂組成物は、更に炭酸カルシウムを前記塩素含有樹脂１００質量部に対して３０質量部以下含有することを特徴とする請求項１～８のいずれかに記載の塩素含有樹脂組成物。 The chlorine-containing resin composition according to any one of claims 1 to 8, wherein the chlorine-containing resin composition further contains calcium carbonate in an amount of 30 parts by mass or less based on 100 parts by mass of the chlorine-containing resin.
PCT/JP2018/027947 2017-10-30 2018-07-25 Chlorine-containing resin composition WO2019087479A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07242784A (en) * 1994-03-08 1995-09-19 Sekisui Chem Co Ltd Vinyl chloride resin composition
JPH0940830A (en) * 1995-07-26 1997-02-10 Asahi Denka Kogyo Kk Vinyl chloride-based resin composition
JPH10158451A (en) * 1996-12-02 1998-06-16 Asahi Denka Kogyo Kk Vinyl chloride resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07242784A (en) * 1994-03-08 1995-09-19 Sekisui Chem Co Ltd Vinyl chloride resin composition
JPH0940830A (en) * 1995-07-26 1997-02-10 Asahi Denka Kogyo Kk Vinyl chloride-based resin composition
JPH10158451A (en) * 1996-12-02 1998-06-16 Asahi Denka Kogyo Kk Vinyl chloride resin composition

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