WO2021033399A1 - Chlorine-containing resin composition and molded product thereof - Google Patents

Chlorine-containing resin composition and molded product thereof Download PDF

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Publication number
WO2021033399A1
WO2021033399A1 PCT/JP2020/023376 JP2020023376W WO2021033399A1 WO 2021033399 A1 WO2021033399 A1 WO 2021033399A1 JP 2020023376 W JP2020023376 W JP 2020023376W WO 2021033399 A1 WO2021033399 A1 WO 2021033399A1
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Prior art keywords
chlorine
acid
containing resin
resin composition
mass
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PCT/JP2020/023376
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French (fr)
Japanese (ja)
Inventor
優一 田沼
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堺化学工業株式会社
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Publication of WO2021033399A1 publication Critical patent/WO2021033399A1/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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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 a chlorine-containing resin composition and a molded product thereof.
  • Chlorine-containing resins typified by polyvinyl chloride are widely used in electric wires, pipes, joints, irregular shapes, etc. because they are highly flexible and easy to process, and also have excellent physical properties such as mechanical strength.
  • chlorine-containing resin has a problem in heat resistance (also called thermal stability), and is unstable to heat during processing and use, and is decomposed by heating to generate hydrogen chloride and chlorine gas. From the viewpoint of improving workability, a stabilizer is usually used together with the chlorine-containing resin.
  • CaZn-based stabilizers Due to the recent increase in awareness of environmental issues, it is mainly composed of calcium, magnesium, aluminum, and zinc compounds in place of the lead-based stabilizers or organic tin-based stabilizers that have been used in recent years.
  • Low-toxicity stabilizers commonly known as CaZn-based stabilizers
  • CaZn stabilizers have a problem in thermal stability as compared with conventional lead-based stabilizers and organotin-based stabilizers, and when injection molding is performed, silver streaks and flashes are generated in the molded product, which causes silver streaks and flashes. Poor appearance and deterioration of physical properties are major problems and issues.
  • zinc oxide particles having a predetermined particle size are used as a stabilizer for a halogen-containing resin such as a chlorine-containing resin as a stabilizer having low toxicity and excellent heat resistance (patent).
  • a halogen-containing resin such as a chlorine-containing resin
  • a stabilizer having low toxicity and excellent heat resistance Patent Document 1
  • a chlorine-containing resin composition that suppresses the generation of silver streaks and flashes while using a low-toxicity stabilizer chlorine-containing alkaline earth metal hydroxide having a predetermined ratio of silica-containing coating layer on the surface is contained.
  • a chlorine-containing resin composition containing a predetermined ratio with respect to the resin is disclosed (see Patent Document 2).
  • a stabilizer having low toxicity and excellent heat resistance and the like, and a chlorine-containing resin composition in which the generation of silver streaks and flashes are suppressed while using a stabilizer having low toxicity are disclosed.
  • the molding processing conditions are stricter than those for molding a small-diameter joint, so silver streaks and flashes are more likely to occur.
  • the prior art is insufficient in terms of suppressing the occurrence of these defects. Therefore, there is a demand for a chlorine-containing resin composition having more excellent heat resistance and capable of more sufficiently suppressing the generation of silver streaks and flashes.
  • the present invention provides a chlorine-containing resin composition which is excellent in heat resistance and can sufficiently suppress the generation of silver streaks and flashes even when a low toxicity stabilizer is used.
  • the purpose is excellent in heat resistance and can sufficiently suppress the generation of silver streaks and flashes even when a low toxicity stabilizer is used.
  • the present inventors have investigated a chlorine-containing resin composition that has excellent heat resistance and can sufficiently suppress the generation of silver streaks and flashes even when a low-toxicity stabilizer is used. As a result, the present inventors have investigated a chlorine-containing resin composition.
  • the stabilizer when at least one of magnesium hydroxide or calcium hydroxide coated with silica and fine zinc oxide having a predetermined average particle size are added at a predetermined ratio, the stabilizer has low toxicity as a stabilizer.
  • an agent it is used, it is possible to sufficiently suppress the generation of silver streaks and flashes during injection molding of a large molded product, and it is possible to obtain a molded product having a good appearance. It came to be completed.
  • the chlorine-containing resin composition is characterized by containing zinc oxide having an average particle size of about 0.35 parts by mass of 0.1 to 0.5 ⁇ m.
  • the silica-coated metal hydroxide is preferably silica-coated magnesium hydroxide.
  • the chlorine-containing resin composition preferably has a plasticizer content of 1 part by mass or less with respect to 100 parts by mass of the chlorine-containing resin. That is, it is preferably used for hard materials.
  • the present invention is also a molded product, which comprises using the chlorine-containing resin composition of the present invention.
  • the chlorine-containing resin composition of the present invention has excellent heat resistance and uses a low-toxicity stabilizer to sufficiently suppress the generation of silver streaks and flashes even when an injection-molded article of a large-sized molded article is produced. Since it is possible to produce a good molded product, it can be suitably used as a raw material for various injection molded products including a large injection molded product such as a large joint.
  • the chlorine-containing resin composition of the present invention contains 0.07 to 0.9 parts by mass of silica-coated magnesium hydroxide and / or as a silica-coated metal hydroxide with respect to 100 parts by mass of the chlorine-containing resin. It is characterized by containing silica-coated calcium hydroxide and zinc oxide having an average particle size of 0.1 to 0.5 ⁇ m in 0.02 to 0.35 parts by mass.
  • Injection molding is a method of injecting a molten chlorine-containing resin composition from a nozzle into a mold at once at high pressure, and therefore processing is performed due to friction between the resin composition and the nozzle or friction between the resin compositions. The temperature of the resin composition rises several tens of degrees above the temperature.
  • the chlorine-containing resin composition is heat-resistant by containing silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide and fine zinc oxide having a predetermined particle size in a predetermined ratio. It is excellent in properties, and it is possible to sufficiently suppress the generation of silver streaks and flashes even during injection molding of a large molded product, and it is also possible to suppress the coloring of the obtained molded product.
  • the chlorine-containing resin composition of the present invention has 0.07 to 0.9 parts by mass of silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide as a silica-coated metal hydroxide with respect to 100 parts by mass of the chlorine-containing resin.
  • the content of silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide may be 0.1 to 0.75 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. preferable. It is more preferably 0.1 to 0.5 parts by mass, and even more preferably 0.1 to 0.35 parts by mass.
  • the chlorine-containing resin composition of the present invention may contain zinc oxide having an average particle size of 0.02 to 0.35 parts by mass of 0.1 to 0.5 ⁇ m with respect to 100 parts by mass of the chlorine-containing resin.
  • the content of zinc oxide is preferably 0.05 to 0.3 parts by mass, and more preferably 0.1 to 0.25 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. is there.
  • vinyl chloride resin examples include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymer and vinyl chloride-ethylene-vinyl acetate co-weight.
  • silica-coated magnesium hydroxide silica-coated calcium hydroxide
  • the silica-coated magnesium hydroxide or silica-coated calcium hydroxide contained in the chlorine-containing resin composition of the present invention has at least a part of the surface of magnesium hydroxide or calcium hydroxide. It may be covered with silica, but it is coated with 0.1 to 20 parts by mass of silica in terms of SiO 2 with respect to 100 parts by mass of uncoated magnesium hydroxide or calcium hydroxide. Is preferable. When the resin is coated in such a ratio, heat resistance can be maintained while exerting a sufficient foaming suppressing effect on the resin.
  • silica means a non-hydrous silicon oxide.
  • the chlorine-containing resin composition of the present invention may contain silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide, but preferably contains silica-coated magnesium hydroxide.
  • silica-coated magnesium hydroxide makes the chlorine-containing resin composition of the present invention more excellent in heat resistance.
  • the method of forming a silica coating layer on the surface of magnesium hydroxide or calcium hydroxide is not particularly limited, and each method such as a dry coating method (mechanochemical reaction), a wet precipitation method, or a sol mixed drying method should be adopted.
  • a dry coating method mechanochemical reaction
  • a wet precipitation method or a sol mixed drying method
  • it can be carried out with reference to Japanese Patent Application Laid-Open No. 2010-70681.
  • the zinc oxide contained in the chlorine-containing resin composition of the present invention may have an average particle size of 0.1 to 0.5 ⁇ m, but preferably an average particle size of 0.1 to 0.4 ⁇ m. .. More preferably, the average particle size is 0.1 to 0.3 ⁇ m.
  • the average particle size of zinc oxide can be measured by the method described in Examples described later.
  • Stabilizer examples of the low-toxicity stabilizer contained in the chlorine-containing resin composition of the present invention include zinc organic acid, calcium organic acid, barium organic acid and the like, and one or more of these may be used. Can be done.
  • the organic acid in the above zinc organic acid, calcium organic acid, and barium organic acid is not particularly limited, but for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, 2-ethylhexylic 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, pt -Butyl benzoic acid, dimethyl hydroxy benzoic acid, 3,5-di-t-butyl-4-hydroxy benzoic acid, toluic acid, dimethyl benzoic acid, ethyl benzoic acid, cumic acid, n-propyl benzoic acid, amino benzoic acid, Monovalents of N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, pt-octylsalicylic acid, ellagic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mer
  • Organic carboxylic acids oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorphthalic acid, aminophthalic acid
  • Divalent organic carboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid; etc., as well as monoesters or monoamide compounds of divalent organic carboxylic acids, butanetricarboxylic acids, etc.
  • Di or triesters of trivalent or tetravalent organic carboxylic acids such as butanetetracarboxylic acid, hemmellitic acid, trimellitic acid, merophanic acid, pyromellitic acid; etc., and one or more of these can be mentioned.
  • higher fatty acids having 12 to 20 carbon atoms are preferable.
  • myristic acid, palmitic acid, isostearic acid, zinc salts of stearic acid and the like which have appropriate slipperiness and compatibility with chlorine-containing resin, are preferable.
  • the content of the stabilizer is not particularly limited, and is preferably 0.01 part by mass or more with respect to 100 parts by mass of the chlorine-containing resin. As a result, discoloration of the molded product obtained from the resin composition can be effectively suppressed. More preferably, it is 0.1 part by mass or more. Further, it is preferably 5 parts by mass or less, whereby the heat resistance can be further enhanced, the appearance of the molded product is not further deteriorated, and the color tone is also improved. More preferably, it is 2 parts by mass or less.
  • the chlorine-containing resin composition of the present invention may also contain a filler.
  • the filler also functions as a neutralizer.
  • 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, and magnesium. Examples thereof include salts such as strontium, boron and zirconium, oxides, hydroxides and composite oxides.
  • the salts are not particularly limited, and examples thereof include sulfates, carbonates, hydrochlorides, acetates, nitrates and the like.
  • examples thereof include zinc acid, barium titanate, and talc, and one or more of these can be used.
  • calcium carbonate is preferable.
  • the specific surface area is less than 25 m 2 / g. It is more preferably 23 m 2 / g or less, further preferably 20 m 2 / g or less, particularly preferably 18 m 2 / g or less, and the lower limit is preferably 0.1 m 2 / g or more. More preferably, it is 0.5 m 2 / g or more. If it exceeds the above range, it may have an adverse effect such as plate-out during processing.
  • the resin composition contains a filler
  • its content is not particularly limited, and for example, it is preferably 40 parts by mass or less with respect to 100 parts by mass of the chlorine-containing resin. If it exceeds 40 parts by mass, plate-out may occur. More preferably, it is 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
  • the chlorine-containing resin composition of the present invention may contain other components if necessary.
  • other components include various additives such as processing aids, strengthening agents, lubricants, antioxidants, antioxidants, colorants, and heat-resistant auxiliary agents, and one or more of these are used. be able to.
  • the amount of other components is preferably 15 parts by mass or less with respect to 100 parts by mass of the entire chlorine-containing resin composition. It is more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.
  • the various additives are not particularly limited, and examples of the processing aid include acrylic processing aids such as (meth) acrylic acid ester-based polymers.
  • examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and the like
  • examples of the methacrylic acid ester include methyl methacrylate and methacrylic acid. Examples thereof include ethyl, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.
  • the acrylic processing aid may be a single polymer of the above acrylic acid and / or an ester thereof, or a polymer of methacrylic acid and / or an ester thereof, or a copolymer of two or more kinds.
  • the weight average molecular weight of the polymer is preferably 200,000 to 7 million.
  • examples of commercially available acrylic processing aids include Metabrene P type manufactured by Mitsubishi Rayon, Kaneka PA series manufactured by Kaneka, and Paraloid K series manufactured by Roam & Haas.
  • strengthening agent examples include butadiene-based strengthening agents such as MBS (methyl methacrylate-butadiene styrene copolymer), chlorinated polyethylene and the like.
  • Lubricants include, for example, liquid paraffins, industrial white mineral oils, synthetic paraffins, petroleum waxes, petrolatum; odorless light hydrocarbons, silicone organopolysiloxanes, fatty acids, aliphatic alcohols, higher fatty acids, animal or vegetable fats and oils. Hydrogenated fatty acids and those fatty acids with 8 to 22 carbon atoms; linear hydroxy fatty acids such as hydroxystearic acid; reducing animal, vegetable fats and oils or their fatty acid esters or decomposing and distilling natural wax.
  • antioxidants examples include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphite-based antioxidant.
  • phenolic antioxidant examples include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditertiary butyl-4-hydroxy).
  • sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl, dimyristyl and distearyl of thiodipropionic acid, and ⁇ - of polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). Examples thereof include alkyl mercaptopropionic acid esters.
  • phosphite-based antioxidant examples include trisnonylphenyl phosphite, tris (2,4-dithiary butylphenyl) phosphite, and tris [2-third butyl-4- (3-third butyl-4).
  • phosphite tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, monodecyldiphenylphosphite, mono (dinonylphenyl) bis (Nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditrimeric butylphenyl) pentaerythritol Diphosphite, bis (2,6-ditetrabutyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridec
  • colorants include TiO 2 , zirconium oxide, BaSO 4 , lithopon (mixture of zinc sulfide and barium sulfate), carbon black, mixture of carbon black and titanium dioxide, iron oxide, Sb 2 O 3 , Cr 2 O. 3.
  • examples thereof include inorganic pigments such as spinel such as cobalt blue and cobalt green and ultramarine blue, and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments. Further, a composite pigment obtained by combining the above pigments can also be mentioned.
  • heat-resistant auxiliary agent examples include hydrotalcite, zeolite, polyhydric alcohol compounds such as dipentaerythritol, partial esters of dipentaerythritol and adipic acid, polyols, tris (2-hydroxyethyl) isocyanurate and the like. Be done.
  • anti-primary agent examples include ⁇ -diketone compounds. Specifically, acetylacetone, ethyl acetoacetate, dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene and the like, or metals thereof. Examples thereof include salts (lithium, sodium, potassium, calcium, magnesium, barium, zinc, etc.).
  • the content of the plasticizer is preferably 1 part by mass or less with respect to 100 parts by mass of the chlorine-containing resin. Poor appearance is likely to occur in the case of a molded product obtained from a hard resin composition having a low content of plasticizer. Therefore, when the resin composition is a hard type having a low content of the plasticizer, the effect of the present invention will be exhibited more remarkably.
  • the content of the plasticizer is more preferably 0.1% by weight or less, and further preferably not contained.
  • the present invention is also a molded article using the chlorine-containing resin composition of the present invention described above, that is, a molded article formed from the chlorine-containing resin composition of the present invention.
  • a molded product has excellent heat resistance, and is a molded product with few appearance defects in which the generation of silver streaks and flashes is sufficiently suppressed.
  • the molding method (molding method) for obtaining the molded product is not particularly limited, and examples thereof include extrusion molding, injection molding, roll molding, dip molding, and blow molding.
  • examples thereof include extrusion molding, injection molding, roll molding, dip molding, and blow molding.
  • the chlorine-containing resin composition of the present invention sufficiently suppresses the generation of silver streaks and flashes during injection molding, a molded product is produced by injection molding among the above molding methods. Is a preferred embodiment of the present invention.
  • the molded body is a pipe or a joint.
  • the joint since the joint usually has a complicated shape, it is usually formed at a high temperature.
  • An injection molding machine is used as the processing molding machine.
  • the resin composition of the present invention has the heat resistance required for injection molding, and the generation of silver streaks and flashes during injection molding is sufficiently suppressed. Therefore, the above molding is thus performed.
  • the form in which the body is a joint is one of the preferred forms of the present invention, and the form in which the molded body is a large-sized joint is particularly preferable.
  • the large joint refers to a joint for connecting pipes having a diameter of 30 mm or more.
  • the average particle size of zinc oxide was measured by the following method. ⁇ Measurement of average particle size> Zinc oxide was added to an aqueous solution of sodium hexametaphosphate as a dispersion medium, and the measurement was performed using a laser diffraction / scattering method particle size distribution measuring device (manufactured by BECKMAN COOLTER, product name: LS 13 320).
  • Dispersion medium Sodium hexametaphosphate aqueous solution Measurement upper limit: 2000 ⁇ m Lower limit of measurement: 0.017 ⁇ m Particle refractive index: 2.00 Particle shape: Non-spherical solvent Refractive index: 1.333
  • (C) Silica-coated magnesium hydroxide Magnesium hydroxide particles according to the synthetic example.
  • Examples 1-12, Comparative Examples 1-12 The additives shown in Tables 1 and 2 were added to 100 parts by mass of the vinyl chloride resin.
  • the obtained vinyl chloride resin composition was kneaded with an 8-inch roll machine (manufactured by KANSAI ROLL) adjusted to a roll surface temperature of 170 ° C. for 5 minutes to prepare a roll sheet having a thickness of 0.3 mm. Using this sheet, each test was conducted below. The results are shown in Tables 1 and 2.
  • the YI value was determined with a color difference meter on the sheet after pressing. Since it may be difficult to see the difference in heat resistance from the YI value, the degree of change in yellowing, browning, and blackening was visually determined, and at the same time, the amount of bubbles generated on the press sheet was also determined. Heat resistance and foamability were judged according to the following criteria.
  • the chlorine-containing resin composition contains silica-coated magnesium hydroxide and zinc oxide in a predetermined ratio, respectively, to have excellent heat resistance and suppress the foaming of the resin. confirmed. Since silver streaks and flashes are caused by foaming of the resin, from this result, the chlorine-containing resin composition of the present invention has excellent heat resistance and can sufficiently suppress the generation of silver streaks and flashes. It was confirmed that it was a resin composition.

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Abstract

The present invention addresses the problem of providing a chlorine-containing resin composition which has excellent heat resistance and can be satisfactorily prevented from the formation of silver streaks or flashes even when a low-toxic stabilizing agent is used. The present invention is a chlorine-containing resin composition which contains silica-coated magnesium hydroxide and/or silica-coated calcium hydroxide, as a silica-coated metal hydroxide, in an amount of 0.07 to 0.9 part by mass and zinc oxide having an average particle diameter of 0.1 to 0.5 μm in an amount of 0.02 to 0.35 parts by mass both relative to 100 parts by mass of the chlorine-containing resin.

Description

塩素含有樹脂組成物及びその成形体Chlorine-containing resin composition and its molded product
本発明は、塩素含有樹脂組成物及びその成形体に関する。 The present invention relates to a chlorine-containing resin composition and a molded product thereof.
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、機械的強度等の物性にも優れるため、電線、パイプ、継手、異型等の用途に広く使用されている。一方で、塩素含有樹脂は耐熱性（熱安定性ともいう）に課題があり、加工時や使用時の熱に不安定で加熱により分解が生じ、塩化水素や塩素ガスが発生するため、耐熱性や加工性向上の観点から、塩素含有樹脂とともに安定剤が併用されるのが通常である。 Chlorine-containing resins typified by polyvinyl chloride are widely used in electric wires, pipes, joints, irregular shapes, etc. because they are highly flexible and easy to process, and also have excellent physical properties such as mechanical strength. On the other hand, chlorine-containing resin has a problem in heat resistance (also called thermal stability), and is unstable to heat during processing and use, and is decomposed by heating to generate hydrogen chloride and chlorine gas. From the viewpoint of improving workability, a stabilizer is usually used together with the chlorine-containing resin.
昨今の環境問題への意識の高まりにより、近年は従来から使用されてきた鉛系安定剤または有機錫系安定剤に代えて、主にカルシウムやマグネシウム、アルミニウム、亜鉛の各化合物から構成されている低毒性の安定化剤（通称ＣａＺｎ系安定剤）が使用されることが多くなってきている。しかし、ＣａＺｎ安定剤は、従来の鉛系安定剤や有機錫系安定剤と比較すると熱安定性に課題があり、射出成形を行った場合に成形体にシルバーストリークやフラッシュを発生させ、これらによる外観不良や物性低下が大きな問題、課題となっている。これに対し、低毒性であって耐熱性等に優れた安定剤として、所定の粒子径の酸化亜鉛粒子を塩素含有樹脂等のハロゲン含有樹脂の安定剤として使用することが開示されている（特許文献１参照）。また、低毒性の安定化剤を使用しながらシルバーストリークやフラッシュの発生を抑制した塩素含有樹脂組成物として、所定の割合のシリカ含有被覆層を表面に有するアルカリ土類金属水酸化物を塩素含有樹脂に対して所定の割合で含む塩素含有樹脂組成物が開示されている（特許文献２参照）。 Due to the recent increase in awareness of environmental issues, it is mainly composed of calcium, magnesium, aluminum, and zinc compounds in place of the lead-based stabilizers or organic tin-based stabilizers that have been used in recent years. Low-toxicity stabilizers (commonly known as CaZn-based stabilizers) are increasingly used. However, CaZn stabilizers have a problem in thermal stability as compared with conventional lead-based stabilizers and organotin-based stabilizers, and when injection molding is performed, silver streaks and flashes are generated in the molded product, which causes silver streaks and flashes. Poor appearance and deterioration of physical properties are major problems and issues. On the other hand, it is disclosed that zinc oxide particles having a predetermined particle size are used as a stabilizer for a halogen-containing resin such as a chlorine-containing resin as a stabilizer having low toxicity and excellent heat resistance (patent). Reference 1). Further, as a chlorine-containing resin composition that suppresses the generation of silver streaks and flashes while using a low-toxicity stabilizer, chlorine-containing alkaline earth metal hydroxide having a predetermined ratio of silica-containing coating layer on the surface is contained. A chlorine-containing resin composition containing a predetermined ratio with respect to the resin is disclosed (see Patent Document 2).
特開２００６－１２４５０２号公報Japanese Unexamined Patent Publication No. 2006-124502 特開２０１０－７０６８１号公報Japanese Unexamined Patent Publication No. 2010-70681
上記のとおり、低毒性であって耐熱性等に優れた安定剤や、低毒性の安定化剤を使用しながらシルバーストリークやフラッシュの発生を抑制した塩素含有樹脂組成物が開示されている。しかし、本発明者の検討によると、射出成形で大口径継手等の大型成形体を作製する場合、小口径継手の成形に比べて成形加工条件が厳しいため、シルバーストリーク、フラッシュがより発生しやすくなり、従来技術ではこれらの不具合の発生抑制の点で不十分であるとことが判明した。このため、より耐熱性が優れるとともに、シルバーストリーク、フラッシュの発生をより十分に抑制することができる塩素含有樹脂組成物が求められている。 As described above, a stabilizer having low toxicity and excellent heat resistance and the like, and a chlorine-containing resin composition in which the generation of silver streaks and flashes are suppressed while using a stabilizer having low toxicity are disclosed. However, according to the study of the present inventor, when a large-sized molded body such as a large-diameter joint is manufactured by injection molding, the molding processing conditions are stricter than those for molding a small-diameter joint, so silver streaks and flashes are more likely to occur. As a result, it was found that the prior art is insufficient in terms of suppressing the occurrence of these defects. Therefore, there is a demand for a chlorine-containing resin composition having more excellent heat resistance and capable of more sufficiently suppressing the generation of silver streaks and flashes.
本発明は、上記現状に鑑み、低毒性の安定化剤を使用した場合でも、耐熱性に優れ、シルバーストリークやフラッシュの発生を十分に抑制することができる塩素含有樹脂組成物を提供することを目的とする。 In view of the above situation, the present invention provides a chlorine-containing resin composition which is excellent in heat resistance and can sufficiently suppress the generation of silver streaks and flashes even when a low toxicity stabilizer is used. The purpose.
本発明者らは、低毒性の安定化剤を使用した場合でも、耐熱性に優れ、シルバーストリークやフラッシュの発生を十分に抑制することができる塩素含有樹脂組成物について検討したところ、塩素含有樹脂に対して、シリカで被覆された水酸化マグネシウム又は水酸化カルシウムの少なくとも１つと、所定の平均粒子径を有する微細な酸化亜鉛とをそれぞれ所定の割合で添加すると、安定剤として低毒性の安定化剤を使用した場合でも、大型成形体の射出成形時におけるシルバーストリークやフラッシュの発生を十分に抑制することができ、外観の良好な成形体を得ることが可能となることを見出し、本発明を完成するに至った。 The present inventors have investigated a chlorine-containing resin composition that has excellent heat resistance and can sufficiently suppress the generation of silver streaks and flashes even when a low-toxicity stabilizer is used. As a result, the present inventors have investigated a chlorine-containing resin composition. On the other hand, when at least one of magnesium hydroxide or calcium hydroxide coated with silica and fine zinc oxide having a predetermined average particle size are added at a predetermined ratio, the stabilizer has low toxicity as a stabilizer. We have found that even when an agent is used, it is possible to sufficiently suppress the generation of silver streaks and flashes during injection molding of a large molded product, and it is possible to obtain a molded product having a good appearance. It came to be completed.
すなわち本発明は、塩素含有樹脂１００質量部に対して、シリカ被覆金属水酸化物として０．０７～０．９質量部のシリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムと、０．０２～０．３５質量部の平均粒子径が０．１～０．５μｍである酸化亜鉛とを含むことを特徴とする塩素含有樹脂組成物である。 That is, in the present invention, 0.07 to 0.9 parts by mass of silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide and 0.02 as silica-coated metal hydroxide with respect to 100 parts by mass of chlorine-containing resin. The chlorine-containing resin composition is characterized by containing zinc oxide having an average particle size of about 0.35 parts by mass of 0.1 to 0.5 μm.
上記シリカ被覆金属水酸化物は、シリカ被覆水酸化マグネシウムであることが好ましい。 The silica-coated metal hydroxide is preferably silica-coated magnesium hydroxide.
上記塩素含有樹脂組成物は、可塑剤の含有量が塩素含有樹脂１００質量部に対して、１質量部以下であることが好ましい。すなわち、硬質系材料に用いることが好ましい。 The chlorine-containing resin composition preferably has a plasticizer content of 1 part by mass or less with respect to 100 parts by mass of the chlorine-containing resin. That is, it is preferably used for hard materials.
本発明はまた、本発明の塩素含有樹脂組成物を用いてなることを特徴とする成形体でもある。 The present invention is also a molded product, which comprises using the chlorine-containing resin composition of the present invention.
本発明の塩素含有樹脂組成物は耐熱性に優れ、低毒性の安定化剤を使用し、大型成形体の射出成形体を作製した場合においてもシルバーストリークやフラッシュの発生を十分に抑制し、外観の良好な成形体を製造することができることから、大型継手等の大型の射出成形体を含む各種射出成形体の原料として好適に使用することができる。 The chlorine-containing resin composition of the present invention has excellent heat resistance and uses a low-toxicity stabilizer to sufficiently suppress the generation of silver streaks and flashes even when an injection-molded article of a large-sized molded article is produced. Since it is possible to produce a good molded product, it can be suitably used as a raw material for various injection molded products including a large injection molded product such as a large joint.
以下、本発明の好ましい形態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において適宜変更して適用することができる。 Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention.
１．塩素含有樹脂組成物
本発明の塩素含有樹脂組成物は、塩素含有樹脂１００質量部に対して、シリカ被覆金属水酸化物として０．０７～０．９質量部のシリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムと、０．０２～０．３５質量部の平均粒子径が０．１～０．５μｍである酸化亜鉛とを含むことを特徴とする。
射出成形は、溶融した塩素含有樹脂組成物をノズルから高圧で金型に一気に射出して成形する方法であることから、樹脂組成物とノズルとの摩擦又は樹脂組成物同士の摩擦のため、加工温度より数十度樹脂組成物の温度が上昇する。それゆえ、極めて高レベルの耐熱性が要求される。近年使用が増えている低毒性の安定化剤は、熱安定性に課題があり、射出成形時にシルバーストリークやフラッシュが発生する原因となるが、射出成形機が小型であれば、射出圧（背圧）が小さく、また成形機中での滞留時間が短いため、シリカ被覆水酸化マグネシウム等を添加することで塩素含有樹脂組成物に耐熱性を付与し、シルバーストリークやフラッシュの発生をある程度抑えることができる。しかし、射出成形で大型の製品をつくる場合、シリンダー内に多量の塩素含有樹脂を入れ、溶融粘度が十分に低下するように加熱し続けるため、塩素含有樹脂が加熱される時間が長くなり、その間に塩素含有樹脂はシリカ被覆水酸化マグネシウム等により付与された耐熱の限界を超え、塩化水素等の発生量が増大する。ここで増大した塩化水素は水酸化マグネシウムや水酸化カルシウムと反応し、水分が発生する。また、大型製品の製造時には射出機の背圧も大きくなるのでノズル先端で樹脂に大きな摩擦が発生して発熱するが、この時点では低毒性の安定化剤の耐熱付与能力は相当低下しているためこれも樹脂からの大幅な脱塩化水素及び水分発生の原因となる。塩化水素及び水分があると樹脂が発泡し、成形体にシルバーストリークやフラッシュが発生する。
これに対し、塩素含有樹脂組成物がシリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムと所定の粒子径の微細な酸化亜鉛をそれぞれ所定の割合で含むことで、塩素含有樹脂組成物を耐熱性に優れ、かつ、大型成形体の射出成形時においてもシルバーストリークやフラッシュの発生を十分に抑制されたものとすることができ、また得られる成形体の着色も抑制することができる。 1. 1. Chlorine-containing resin composition The chlorine-containing resin composition of the present invention contains 0.07 to 0.9 parts by mass of silica-coated magnesium hydroxide and / or as a silica-coated metal hydroxide with respect to 100 parts by mass of the chlorine-containing resin. It is characterized by containing silica-coated calcium hydroxide and zinc oxide having an average particle size of 0.1 to 0.5 μm in 0.02 to 0.35 parts by mass.
Injection molding is a method of injecting a molten chlorine-containing resin composition from a nozzle into a mold at once at high pressure, and therefore processing is performed due to friction between the resin composition and the nozzle or friction between the resin compositions. The temperature of the resin composition rises several tens of degrees above the temperature. Therefore, an extremely high level of heat resistance is required. Low-toxicity stabilizers, which have been increasingly used in recent years, have problems with thermal stability and cause silver streaks and flashes during injection molding. However, if the injection molding machine is small, the injection pressure (back) Since the pressure) is small and the residence time in the molding machine is short, heat resistance is imparted to the chlorine-containing resin composition by adding silica-coated magnesium hydroxide, etc., and the occurrence of silver streaks and flashes is suppressed to some extent. Can be done. However, when making a large product by injection molding, a large amount of chlorine-containing resin is put in the cylinder and heating is continued so that the melt viscosity is sufficiently lowered, so that the chlorine-containing resin is heated for a long time, and during that time. In addition, the chlorine-containing resin exceeds the heat resistance limit imparted by silica-coated magnesium hydroxide or the like, and the amount of hydrogen chloride or the like generated increases. The increased hydrogen chloride reacts with magnesium hydroxide and calcium hydroxide to generate water. In addition, when manufacturing large products, the back pressure of the injection machine also increases, so large friction is generated in the resin at the tip of the nozzle and heat is generated, but at this point the heat resistance imparting ability of the low toxicity stabilizer is considerably reduced. Therefore, this also causes a large amount of hydrogen chloride and water generation from the resin. The presence of hydrogen chloride and moisture causes the resin to foam, causing silver streaks and flashes in the molded product.
On the other hand, the chlorine-containing resin composition is heat-resistant by containing silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide and fine zinc oxide having a predetermined particle size in a predetermined ratio. It is excellent in properties, and it is possible to sufficiently suppress the generation of silver streaks and flashes even during injection molding of a large molded product, and it is also possible to suppress the coloring of the obtained molded product.
本発明の塩素含有樹脂組成物は、塩素含有樹脂１００質量部に対して、シリカ被覆金属水酸化物として０．０７～０．９質量部のシリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムを含むものであればよいが、シリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムの含有量は、塩素含有樹脂１００質量部に対して、０．１～０．７５質量部であることが好ましい。より好ましくは、０．１～０．５質量部であり、更に好ましくは、０．１～０．３５質量部である。 The chlorine-containing resin composition of the present invention has 0.07 to 0.9 parts by mass of silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide as a silica-coated metal hydroxide with respect to 100 parts by mass of the chlorine-containing resin. However, the content of silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide may be 0.1 to 0.75 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. preferable. It is more preferably 0.1 to 0.5 parts by mass, and even more preferably 0.1 to 0.35 parts by mass.
本発明の塩素含有樹脂組成物は、塩素含有樹脂１００質量部に対して、０．０２～０．３５質量部の平均粒子径が０．１～０．５μｍである酸化亜鉛を含むものであればよいが、酸化亜鉛の含有量は、塩素含有樹脂１００質量部に対して、好ましくは、０．０５～０．３質量部であり、より好ましくは、０．１～０．２５質量部である。 The chlorine-containing resin composition of the present invention may contain zinc oxide having an average particle size of 0.02 to 0.35 parts by mass of 0.1 to 0.5 μm with respect to 100 parts by mass of the chlorine-containing resin. However, the content of zinc oxide is preferably 0.05 to 0.3 parts by mass, and more preferably 0.1 to 0.25 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. is there.
１）塩素含有樹脂
本発明の塩素含有樹脂組成物が含む塩素含有樹脂としては、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。 1) Chlorine-containing resin The chlorine-containing resin contained in the chlorine-containing resin composition of the present invention is not particularly limited as long as it is a resin (polymer) containing a chlorine atom, but a vinyl chloride-based resin is preferable. As a result, a molded product having excellent flexibility and flame retardancy can be 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、これらの１種又は２種以上を用いることができる。
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 the vinyl chloride resin include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymer and vinyl chloride-ethylene-vinyl acetate co-weight. Combined, 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 acid 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 copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, chloride Copolymers such as vinyl-maleimide copolymer; and the like; one or more of these can be used.
A blended product of a chlorine-containing resin and a chlorine-free resin may be used, and the polymerization method for obtaining a vinyl chloride-based resin is not particularly limited.
２）シリカ被覆水酸化マグネシウム、シリカ被覆水酸化カルシウム
本発明の塩素含有樹脂組成物が含むシリカ被覆水酸化マグネシウムやシリカ被覆水酸化カルシウムは、水酸化マグネシウムや水酸化カルシウムの表面の少なくとも一部がシリカによって覆われているものであればよいが、未被覆の水酸化マグネシウムや水酸化カルシウム１００質量部に対して、ＳｉＯ２換算で０．１～２０質量部のシリカで被覆されたものであることが好ましい。このような割合で被覆されたものであることで、樹脂に対し、十分な発泡抑制効果を発揮しながら耐熱性を維持できる。より好ましくは、未被覆の水酸化マグネシウムや水酸化カルシウム１００質量部に対して、ＳｉＯ２換算で０．１～１５質量部のシリカで被覆されたものであり、更に好ましくは、ＳｉＯ２換算で８～１２質量部のシリカで被覆されたものである。
なお、本発明において「シリカ」とは、非含水のケイ素酸化物を意味する。 2) Silica-coated magnesium hydroxide, silica-coated calcium hydroxide The silica-coated magnesium hydroxide or silica-coated calcium hydroxide contained in the chlorine-containing resin composition of the present invention has at least a part of the surface of magnesium hydroxide or calcium hydroxide. It may be covered with silica, but it is coated with 0.1 to 20 parts by mass of silica in terms of SiO 2 with respect to 100 parts by mass of uncoated magnesium hydroxide or calcium hydroxide. Is preferable. When the resin is coated in such a ratio, heat resistance can be maintained while exerting a sufficient foaming suppressing effect on the resin. More preferably, with respect to 100 parts by weight of magnesium and calcium hydroxide uncoated, it has been coated with 0.1 to 15 parts by weight of silica in terms of SiO 2, more preferably, in terms of SiO 2 It is coated with 8 to 12 parts by mass of silica.
In the present invention, "silica" means a non-hydrous silicon oxide.
本発明の塩素含有樹脂組成物は、シリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムを含むものであればよいが、シリカ被覆水酸化マグネシウムを含むことが好ましい。シリカ被覆水酸化マグネシウムを含むことで、本発明の塩素含有樹脂組成物が耐熱性により優れたものとなる。 The chlorine-containing resin composition of the present invention may contain silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide, but preferably contains silica-coated magnesium hydroxide. The inclusion of silica-coated magnesium hydroxide makes the chlorine-containing resin composition of the present invention more excellent in heat resistance.
上記水酸化マグネシウムや水酸化カルシウムの表面にシリカの被覆層を形成する方法は特に限定されず、乾式被覆法（メカノケミカル反応）や湿式沈殿法やゾル混合乾燥法等の各方法を採用することができ、例えば特開２０１０－７０６８１号公報を参照して行うことができる。 The method of forming a silica coating layer on the surface of magnesium hydroxide or calcium hydroxide is not particularly limited, and each method such as a dry coating method (mechanochemical reaction), a wet precipitation method, or a sol mixed drying method should be adopted. For example, it can be carried out with reference to Japanese Patent Application Laid-Open No. 2010-70681.
３）酸化亜鉛
本発明の塩素含有樹脂組成物が含む酸化亜鉛は、平均粒子径が０．１～０．５μｍであればよいが、平均粒子径が０．１～０．４μｍのものが好ましい。より好ましくは、平均粒子径が０．１～０．３μｍのものである。
酸化亜鉛の平均粒子径は、後述する実施例に記載の方法により測定することができる。 3) Zinc oxide The zinc oxide contained in the chlorine-containing resin composition of the present invention may have an average particle size of 0.1 to 0.5 μm, but preferably an average particle size of 0.1 to 0.4 μm. .. More preferably, the average particle size is 0.1 to 0.3 μm.
The average particle size of zinc oxide can be measured by the method described in Examples described later.
４）安定剤
本発明の塩素含有樹脂組成物が含む低毒性の安定化剤としては、有機酸亜鉛、有機酸カルシウム、有機酸バリウム等が挙げられ、これらの１種又は２種以上を用いることができる。 4) Stabilizer Examples of the low-toxicity stabilizer contained in the chlorine-containing resin composition of the present invention include zinc organic acid, calcium organic acid, barium organic acid and the like, and one or more of these may be used. Can be done.
上記有機酸亜鉛、有機酸カルシウム、有機酸バリウム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、これらの１種又は２種以上を用いることができる。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 above zinc organic acid, calcium organic acid, and barium organic acid is not particularly limited, but for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, 2-ethylhexylic 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, pt -Butyl benzoic acid, dimethyl hydroxy benzoic acid, 3,5-di-t-butyl-4-hydroxy benzoic acid, toluic acid, dimethyl benzoic acid, ethyl benzoic acid, cumic acid, n-propyl benzoic acid, amino benzoic acid, Monovalents of N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, pt-octylsalicylic acid, ellagic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid, etc. Organic carboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorphthalic acid, aminophthalic acid Divalent organic carboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid; etc., as well as monoesters or monoamide compounds of divalent organic carboxylic acids, butanetricarboxylic acids, etc. Di or triesters of trivalent or tetravalent organic carboxylic acids such as butanetetracarboxylic acid, hemmellitic acid, trimellitic acid, merophanic acid, pyromellitic acid; etc., and one or more of these can be mentioned. Can be used. Of these, 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 slipperiness and compatibility with chlorine-containing resin, are preferable.
上記安定剤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、樹脂組成物から得られる成形体の変色を効果的に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 stabilizer is not particularly limited, and is preferably 0.01 part by mass or more with respect to 100 parts by mass of the chlorine-containing resin. As a result, discoloration of the molded product obtained from the resin composition can be effectively suppressed. More preferably, it is 0.1 part by mass or more. Further, it is preferably 5 parts by mass or less, whereby the heat resistance can be further enhanced, the appearance of the molded product is not further deteriorated, and the color tone is also improved. More preferably, it is 2 parts by mass or less.
５）充填剤
本発明の塩素含有樹脂組成物はまた、充填剤を含んでも良い。充填剤は中和剤としても機能する。 5) Filler The chlorine-containing resin composition of the present invention may also contain a filler. The filler also functions as a neutralizer.
上記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、塩酸塩、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、これらの１種又は２種以上を用いることができる。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, and magnesium. Examples thereof include salts such as strontium, boron and zirconium, oxides, hydroxides and composite oxides. The salts are not particularly limited, and examples thereof include sulfates, carbonates, hydrochlorides, acetates, nitrates and the like. Specifically, for example, calcium carbonate, zinc carbonate, magnesium carbonate, silica, titanium oxide, cerium oxide, iron oxide, barium sulfate, strontium sulfate, magnesium sulfate, silicon oxide, aluminum oxide, magnesium oxide, zinc silicate, titanium. Examples thereof include zinc acid, barium titanate, and talc, and one or more of these can be used. Of these, calcium carbonate is preferable.
炭酸カルシウムを使用する場合は、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。 When calcium carbonate is used, it is preferable that the specific surface area (BET specific surface area) is less than 25 m 2 / g. It is more preferably 23 m 2 / g or less, further preferably 20 m 2 / g or less, particularly preferably 18 m 2 / g or less, and the lower limit is preferably 0.1 m 2 / g or more. More preferably, it is 0.5 m 2 / g or more. If it exceeds the above range, it may have an adverse effect such as plate-out 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を生じる恐れがある。より好ましくは、２０質量部以下、特に好ましくは１０質量部以下である。 When the resin composition contains a filler, its content is not particularly limited, and for example, it is preferably 40 parts by mass or less with respect to 100 parts by mass of the chlorine-containing resin. If it exceeds 40 parts by mass, plate-out may occur. More preferably, it is 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
６）他の成分
本発明の塩素含有樹脂組成物は、必要に応じてその他の成分を含んでもよい。その他の成分としては例えば、加工助剤、強化剤、滑剤、初着防止剤、酸化防止剤、着色剤、耐熱助剤等の各種添加剤が挙げられ、これらの１種又は２種以上を用いることができる。 6) Other components The chlorine-containing resin composition of the present invention may contain other components if necessary. Examples of other components include various additives such as processing aids, strengthening agents, lubricants, antioxidants, antioxidants, colorants, and heat-resistant auxiliary agents, and one or more of these are used. be able to.
その他の成分の量は、塩素含有樹脂組成物全体１００質量部に対して、それぞれ１５質量部以下であることが好ましい。より好ましくは、１０質量部以下であり、更に好ましくは、５質量部以下である。 The amount of other components is preferably 15 parts by mass or less with respect to 100 parts by mass of the entire chlorine-containing resin composition. It is more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.
各種添加剤はそれぞれ特に限定されないが、加工助剤としては、例えば、（メタ）アクリル酸エステル系重合体等のアクリル系加工助剤が挙げられる。アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸２－エチルヘキシル、アクリル酸シクロヘキシル等が挙げられ、メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸２－エチルヘキシル、メタクリル酸シクロヘキシル等が挙げられる。アクリル系加工助剤は、上記のアクリル酸及び／又はそのエステルや、メタクリル酸及び／又はそのエステルそれぞれの単独の重合体であっても２種以上の共重合体であってもよい。重合体の重量平均分子量は２０万～７００万であることが好ましい。
上記アクリル系加工助剤の市販品としては、例えば、三菱レイヨン製のメタブレンＰタイプ、カネカ製のカネエースＰＡシリーズ、ローム・アンド・ハース製のパラロイドＫシリーズ等が挙げられる。 The various additives are not particularly limited, and examples of the processing aid include acrylic processing aids such as (meth) acrylic acid ester-based polymers. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and the like, and examples of the methacrylic acid ester include methyl methacrylate and methacrylic acid. Examples thereof include ethyl, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. The acrylic processing aid may be a single polymer of the above acrylic acid and / or an ester thereof, or a polymer of methacrylic acid and / or an ester thereof, or a copolymer of two or more kinds. The weight average molecular weight of the polymer is preferably 200,000 to 7 million.
Examples of commercially available acrylic processing aids include Metabrene P type manufactured by Mitsubishi Rayon, Kaneka PA series manufactured by Kaneka, and Paraloid K series manufactured by Roam & Haas.
強化剤としては、例えば、ＭＢＳ（メチルメタクリレート－ブタジエンスチレン共重合体）等のブタジエン系強化剤、塩素化ポリエチレン等が挙げられる。 Examples of the strengthening agent include butadiene-based strengthening agents such as MBS (methyl methacrylate-butadiene styrene copolymer), chlorinated polyethylene and the like.
滑剤としては、例えば、流動パラフィン、工業用白色鉱油、合成パラフィン、石油系ワックス、ペトロラタム；無臭軽質炭化水素、シリコーンオルガノポリシロキサン、脂肪酸、脂肪族アルコール、高級脂肪酸、動物又は植物油脂から得られた脂肪酸及びそれらの脂肪酸を水素添加したもので、炭素数が８～２２のもの；ヒドロキシステアリン酸等の直鎖ヒドロキシ脂肪酸；動物、植物油脂又はそれらの脂肪酸エステルを還元又は天然ロウを分解蒸留して得られる炭素数４以上のもの；トリデシルアルコール、ポリエチレングリコールで分子量２００～９５００のもの；ポリプロピレングリコールで分子量１０００以上のもの；ポリオキシプロピレン－ポリオキシエチレン－ブロック重合体で分子量１９００～９０００のもの；の他、オレイルパルミトアマイド、ステアリルエルカ酸アマイド、２ステアロアミドエチルステアレート、エチレンビス脂肪酸アマイド、Ｎ，Ｎ’－オレオイルステアリルエチレンジアミン、Ｎ，Ｎ’ －ビス（２ヒドロキシエチル）アルキル（Ｃ１２～Ｃ１８）アマイド、Ｎ，Ｎ’ビス（ヒドロキシエチル）ラウロアマイド、Ｎ－アルキル（Ｃ１６～Ｃ１８）トリメチレンジアミンと反応したオレイン酸脂肪酸ジエタノールアミン、ジ（ヒドロキシエチル）ジエチレントリアミンモノアセテートのジステアリン酸エステル、ステアリン酸ｎ－ブチル水添ロジンメチルエステル、セバチン酸ジｎ－ブチル、セバチン酸ジイソブチル、セバチン酸ジ２エチルヘキシル、セバチン酸ジｎ－オクチル、グリセリン脂肪酸エステル、グリセリンラクトステアリル、ペンタエリスリトールステアリン酸モノエステル、ペンタエリスリトールステアリン酸ジエステル、ペンタエリスリトールステアリン酸トリエステル、ペンタエリスリトールステアリン酸テトラエステル、ソルビタン脂肪酸エステル、ポリエチレングリコールモノステアレート、ポリエチレングリコールジラウレート、ポリエチレングリコールモノオレエート、ポリエチレングリコールジオレエート、ポリエチレングリコールヤシ脂肪酸エステル、ポリエチレングリコールトール油脂肪酸エステル、エタンジオールモンタン酸エステル、１，３ブタンジオールモンタン酸エステル、ジエチレングリコールステアリン酸エステル、プロピレングリコール脂肪酸エステル、トリグリセライド、アマニ油、パーム油、１２－ヒドロオキシステアリン酸のグリセリンエステル、水添魚油、牛脂、スパームアセチワックス、モンタンワックス、カルナバワックス、密蝋、木蝋、硬化鯨油ラウリルステアレート、ステアリルステアレートなど一価脂肪族アルコールの脂肪族飽和酸エステル、ラノリン、ステアリン酸亜鉛、ステアリン酸カルシウムなど高級脂肪酸のアルカリ金属、アルカリ土類金属の塩、低分子量ポリエチレン、低分子量ポリプロピレン、酸化ポリエチレン、フッ素系樹脂、ポリ４フッ化エチレン、４フッ化エチレン／６フッ化プロピレン共重合体、ポリ塩化３フッ化エチレン、ポリフッ化ビニル、その他プロピレングリコールアルギネート、ジアルキルケトン、アクリルコポリマー（例えばＡｌｌｎｅｘ製モダフロー等）が挙げられる。 Lubricants include, for example, liquid paraffins, industrial white mineral oils, synthetic paraffins, petroleum waxes, petrolatum; odorless light hydrocarbons, silicone organopolysiloxanes, fatty acids, aliphatic alcohols, higher fatty acids, animal or vegetable fats and oils. Hydrogenated fatty acids and those fatty acids with 8 to 22 carbon atoms; linear hydroxy fatty acids such as hydroxystearic acid; reducing animal, vegetable fats and oils or their fatty acid esters or decomposing and distilling natural wax. Obtained having 4 or more carbon atoms; tridecyl alcohol, polyethylene glycol having a molecular weight of 200 to 9500; polypropylene glycol having a molecular weight of 1000 or more; polyoxypropylene-polyoxyethylene-block polymer having a molecular weight of 1900 to 9000 In addition, oleyl palmitoamide, stearyl erucate amide, 2 stearoamide ethyl stearate, ethylene bis fatty acid amide, N, N'-oleyl stearyl ethylenediamine, N, N'-bis (2 hydroxyethyl) alkyl ( C12-C18) amide, N, N'bis (hydroxyethyl) lauroamide, oleate fatty acid diethanolamine reacted with N-alkyl (C16-C18) trimethylenediamine, di-(hydroxyethyl) diethylenetriamine monoacetate distearate, stearic acid Acid n-butyl hydrogenated rosin methyl ester, di n-butyl sebatate, diisobutyl sebatate, didiethylhexyl sebatate, din-octyl sebatate, glycerin fatty acid ester, glycerin lactostearyl, pentaerythritol stearic acid monoester, penta Ellislitol stearic acid diester, pentaerythritol stearic acid triester, pentaerythritol stearic acid tetraester, sorbitan fatty acid ester, polyethylene glycol monostearate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol palm fatty acid ester , Polyethylene glycol toll oil fatty acid ester, ethanediol montanic acid ester, 1,3 butanediol montanic acid ester, diethylene glycol stearic acid ester, propylene glycol fatty acid ester, triglyceride, flaxseed oil, palm oil, 12-hydrooxystearic acid Glycerin ester, hydrogenated fish oil, beef fat, palm acetyl wax, montan wax, carnauba wax, dense wax, wood wax, hardened whale oil lauryl stearate, stearyl stearate, etc. Fatty alcohols of monovalent aliphatic alcohols, lanolin, stearic acid Alkali metals of higher fatty acids such as zinc acid and calcium stearate, salts of alkaline earth metals, low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, fluororesin, polytetrafluoroethylene, tetrafluorinated ethylene / hexafluoride propylene Examples thereof include polymers, polyethylene trifluorochloride, polyvinyl fluoride, other propylene glycol alginates, dialkyl ketones, and acrylic copolymers (for example, Modaflow manufactured by Allnex).
酸化防止剤としては、例えば、フェノール系酸化防止剤、硫黄系酸化防止剤、ホスファイト系酸化防止剤が挙げられる。
フェノール系酸化防止剤としては、例えば、２，６－ジ第三ブチル－ｐ－クレゾール、２，６－ジフェニル－４－オクタデシロキシフェノール、ステアリル（３，５－ジ第三ブチル－４－ヒドロキシフェニル）－プロピオネート、ジステアリル（３，５－ジ第三ブチル－４－ヒドロキシベンジル）ホスホネート、チオジエチレングリコールビス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオネート〕、１，６－ヘキサメチレンビス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオネート〕、１，６－ヘキサメチレンビス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオン酸アミド〕、４，４’－チオビス（６－第三ブチル－ｍ－クレゾール）、２，２’－メチレンビス（４－メチル－６－第三ブチルフェノール）、２，２－メチレンビス（４－エチル－６－第三ブチルフェノール）、ビス〔３，３－ビス（４－ヒドロキシ－３－第三ブチルフェニル）ブチリックアシッド〕グリコールエステル、４，４’－ブチリデンビス（６－第三ブチル－ｍ－クレゾール）、２，２’－エチリデンビス（４，６－ジ第三ブチルフェノール）、２，２’－エチリデンビス（４－第二ブチル－６－第三ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－第三ブチルフェニル）ブタン、ビス〔２－第三ブチル－４－メチル－６－（２－ヒドロキシ－３－第三ブチル－５－メチルベンジル）フェニル〕テレフタレート、１，３，５－トリス（２，６－ジメチル－３－ヒドロキシ－４－第三ブチルベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ第三ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ第三ブチル－４－ヒドロキシベンジル）－２，４，６－トリメチルベンゼン、１，３，５－トリス〔（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオニルオキシエチル〕イソシアヌレート、テトラキス〔メチレン－３－（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオネート〕メタン、２－第三ブチル－４－メチル－６－（２－アクリロイルオキシ－３－第三ブチル－５－メチルベンジル）フェノール、３，９－ビス〔１，１－ジメチル－２－｛（３－第三ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝〕エチル－２，４，８，１０－テトラオキサスピロ〔５，５〕ウンデカン、トリエチレングリコールビス〔（３－第三ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート〕等が挙げられる。 Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphite-based antioxidant.
Examples of the phenolic antioxidant include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditertiary butyl-4-hydroxy). Phenyl) -propionate, distearyl (3,5-dithiary butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditritiary butyl-4-hydroxyphenyl) propionate], 1,6- Hexamethylenebis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditriary butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tertiary butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-third butylphenol), 2,2-methylenebis (4-ethyl-6-third) Butylphenol), bis [3,3-bis (4-hydroxy-3-tertiary butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-third butyl-m-cresol), 2,2 '-Etilidenebis (4,6-ditertiary butylphenol), 2,2'-Echilidenbis (4-second butyl-6-third butylphenol), 1,1,3-tris (2-methyl-4- Hydroxy-5-Third Butylphenyl) Butan, Bis [2-Third Butyl-4-Methyl-6- (2-Hydroxy-3-Third Butyl-5-Methylbenzyl) Phenol] Telephthalate, 1, 3, 5 -Tris (2,6-dimethyl-3-hydroxy-4-third butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tertiary butyl-4-hydroxybenzyl) isocyanurate, 1, 3,5-Tris (3,5-di-tertiary butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tertiary butyl-4- Hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-dithiary butyl-4-hydroxyphenyl) propionate] methane, 2-third butyl-4-methyl-6- (2-) Acryloyloxy-3-3 butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-3 butyl-4-hydroxy-5-methylphenyl) propionyloxy} ] Ethyl-2,4,8,10-tetraoxaspiro [5,5] Examples thereof include undecane and triethylene glycol bis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate].
硫黄系酸化防止剤としては、例えば、チオジプロピオン酸のジラウリル、ジミリスチル、ジステアリル等のジアルキルチオジプロピオネート類、及び、ペンタエリスリトールテトラ（β－ドデシルメルカプトプロピオネート）等のポリオールのβ－アルキルメルカプトプロピオン酸エステル類が挙げられる。 Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl and distearyl of thiodipropionic acid, and β- of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples thereof include alkyl mercaptopropionic acid esters.
ホスファイト系酸化防止剤としては、例えば、トリスノニルフェニルホスファイト、トリス（２，４－ジ第三ブチルフェニル）ホスファイト、トリス〔２－第三ブチル－４－（３－第三ブチル－４－ヒドロキシ－５－メチルフェニルチオ）－５－メチルフェニル〕ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、モノデシルジフェニルホスファイト、モノ（ジノニルフェニル）ビス（ノニルフェニル）ホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ第三ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（Ｃ１２－１５混合アルキル）－４，４’－ｎ－ブチリデンビス（２－第三ブチル－５－メチルフェノール）ジホスファイト、ヘキサ（トリデシル）－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－第三ブチルフェニル）ブタントリホスファイト、テトラキス（２，４－ジ第三ブチルフェニル）ビフェニレンジホスホナイト、２，２’－メチレンビス（４，６－ジ第三ブチルフェニル）（オクチル）ホスファイト等が挙げられる。 Examples of the phosphite-based antioxidant include trisnonylphenyl phosphite, tris (2,4-dithiary butylphenyl) phosphite, and tris [2-third butyl-4- (3-third butyl-4). -Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, monodecyldiphenylphosphite, mono (dinonylphenyl) bis (Nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditrimeric butylphenyl) pentaerythritol Diphosphite, bis (2,6-ditetrabutyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyridene diphenol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, Tetra (C12-15 mixed alkyl) -4,4'-n-butylidenebis (2-tertiary butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-) Hydroxy-5-Third Butane Phenyl) Butane Triphosphite, Tetraquis (2,4-Ditheal Butylphenyl) Biphenylenediphosphonite, 2,2'-Methylenebis (4,6-Ditertiary Butylphenyl) (octyl) Examples include phosphite.
着色剤としては、例えば、ＴｉＯ２、酸化ジルコニウム、ＢａＳＯ４、リトポン（硫化亜鉛と硫酸バリウムとの混合物）、カーボンブラック、カーボンブラックと二酸化チタンの混合物、酸化鉄、Ｓｂ２Ｏ３、Ｃｒ２Ｏ３、コバルトブルー、コバルトグリーン等のスピネル、ウルトラマリンブルー等の無機顔料や、アゾ顔料、フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ジケトピロロピロール顔料、アントラキノン顔料等の有機顔料が挙げられる。更に、上記顔料を複合した複合顔料も挙げられる。 Examples of colorants include TiO 2 , zirconium oxide, BaSO 4 , lithopon (mixture of zinc sulfide and barium sulfate), carbon black, mixture of carbon black and titanium dioxide, iron oxide, Sb 2 O 3 , Cr 2 O. 3. Examples thereof include inorganic pigments such as spinel such as cobalt blue and cobalt green and ultramarine blue, and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments. Further, a composite pigment obtained by combining the above pigments can also be mentioned.
耐熱助剤としては、例えば、ハイドロタルサイト、ゼオライト、ジペンタエリスリトール等の多価アルコール化合物、ジペンタエリスリトールとアジピン酸との部分エステル、ポリオール類及びトリス（２－ヒドロキシエチル）イソシアヌレート等が挙げられる。 Examples of the heat-resistant auxiliary agent include hydrotalcite, zeolite, polyhydric alcohol compounds such as dipentaerythritol, partial esters of dipentaerythritol and adipic acid, polyols, tris (2-hydroxyethyl) isocyanurate and the like. Be done.
初着防止剤としては、β－ジケトン化合物類が挙げられる。具体的には、アセチルアセトン、アセト酢酸エチル、ジベンゾイルメタン、ベンゾイルアセトン、ステアロイルベンゾイルメタン、カプロイルベンゾイルメタン、デヒドロ酢酸、トリベンゾイルメタン、１，３－ビス（ベンゾイルアセチル）ベンゼン等、あるいはこれらの金属塩（リチウム、ナトリウム、カリウム、カルシウム、マグネシウム、バリウム、亜鉛等）等が挙げられる。 Examples of the anti-primary agent include β-diketone compounds. Specifically, acetylacetone, ethyl acetoacetate, dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene and the like, or metals thereof. Examples thereof include salts (lithium, sodium, potassium, calcium, magnesium, barium, zinc, etc.).
上記以外のその他の成分として可塑剤があるが、本発明の塩素含有樹脂組成物では可塑剤の含有量が塩素含有樹脂１００質量部に対して、１質量部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体の場合である。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、０．１重量％以下であり、更に好ましくは含まないことである。 There is a plasticizer as another component other than the above, but in the chlorine-containing resin composition of the present invention, the content of the plasticizer is preferably 1 part by mass or less with respect to 100 parts by mass of the chlorine-containing resin. Poor appearance is likely to occur in the case of a molded product obtained from a hard resin composition having a low content of plasticizer. Therefore, when the resin composition is a hard type having a low content of the plasticizer, the effect of the present invention will be exhibited more remarkably. The content of the plasticizer is more preferably 0.1% by weight or less, and further preferably not contained.
２．成形体
本発明はまた、上述した本発明の塩素含有樹脂組成物を用いてなる成形体、すなわち本発明の塩素含有樹脂組成物から形成される成形体でもある。このような成形体は、耐熱性に優れ、また、シルバーストリークやフラッシュの発生が十分に抑制された外観不良の少ない成形体である。 2. 2. Molded article The present invention is also a molded article using the chlorine-containing resin composition of the present invention described above, that is, a molded article formed from the chlorine-containing resin composition of the present invention. Such a molded product has excellent heat resistance, and is a molded product with few appearance defects in which the generation of silver streaks and flashes is sufficiently suppressed.
上記成形体を得るための成形方法（成型方法）は特に限定されず、例えば、押出成形、射出成形、ロール成形、ディップ成形、ブロー成形等が挙げられる。上述したように、本発明の塩素含有樹脂組成物は射出成形時のシルバーストリークやフラッシュの発生が十分に抑制されたものであるから、上記成形方法の中でも射出成形によって成形体が作製されることは本発明の好適な実施形態である。 The molding method (molding method) for obtaining the molded product is not particularly limited, and examples thereof include extrusion molding, injection molding, roll molding, dip molding, and blow molding. As described above, since the chlorine-containing resin composition of the present invention sufficiently suppresses the generation of silver streaks and flashes during injection molding, a molded product is produced by injection molding among the above molding methods. Is a preferred embodiment of the present invention.
上記成形体として更に好ましくは、管、継手である。特に継手は通常、複雑な形状からなるため、高温で成形されるのが通常である。また、加工成形機としては射出成形機が用いられる。上述したとおり、本発明の樹脂組成物は射出成形に要求される耐熱性を有し、更に射出成形時のシルバーストリークやフラッシュの発生が十分に抑制されたものであるから、このように上記成形体が継手である形態は、本発明の好適な形態の１つであり、中でも成形体が大型の継手である形態が特に好適である。
ここで、大型の継手とは、口径が３０ｍｍ以上であるパイプを繋ぐための継手を指す。大型の継手はかなり重く、土中深くに埋設されるため、小型の継手よりはるかに大きな強度、特に耐衝撃性強度が要求される。そこで、通常は強化剤を添加して強度を向上させているが、強化剤は樹脂組成物の溶融粘度を大きくするため加工成形時の温度をことさら高くする必要があり、耐熱性が更に要求される。 More preferably, the molded body is a pipe or a joint. In particular, since the joint usually has a complicated shape, it is usually formed at a high temperature. An injection molding machine is used as the processing molding machine. As described above, the resin composition of the present invention has the heat resistance required for injection molding, and the generation of silver streaks and flashes during injection molding is sufficiently suppressed. Therefore, the above molding is thus performed. The form in which the body is a joint is one of the preferred forms of the present invention, and the form in which the molded body is a large-sized joint is particularly preferable.
Here, the large joint refers to a joint for connecting pipes having a diameter of 30 mm or more. Large joints are fairly heavy and are buried deep in the soil, so they require much greater strength than smaller joints, especially impact resistance. Therefore, usually, a reinforcing agent is added to improve the strength, but the reinforcing agent needs to raise the temperature at the time of processing and molding in order to increase the melt viscosity of the resin composition, and further heat resistance is required. To.
本発明を詳細に説明するために以下に具体例を挙げるが、本発明はこれらの例のみに限定されるものではない。特に断りのない限り、「％」及び「ｗｔ％」とは「重量％（質量％）」を意味する。 Specific examples will be given below to explain the present invention in detail, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "wt%" mean "% by weight (mass%)".
酸化亜鉛の平均粒子径は、以下の方法により測定した。
＜平均粒子径の測定＞
酸化亜鉛を分散媒であるヘキサメタリン酸ナトリウム水溶液に加え、レーザー回折／散乱法粒度分布測定装置（ＢＥＣＫＭＡＮ　ＣＯＵＬＴＥＲ製、製品名：ＬＳ １３ ３２０）を用いて測定した。
［測定条件］
分散媒：ヘキサメタリン酸ナトリウム水溶液
測定上限：２０００μｍ
測定下限：０．０１７μｍ
粒子屈折率：２．００
粒子形状：非球形
溶媒屈折率：１．３３３ The average particle size of zinc oxide was measured by the following method.
<Measurement of average particle size>
Zinc oxide was added to an aqueous solution of sodium hexametaphosphate as a dispersion medium, and the measurement was performed using a laser diffraction / scattering method particle size distribution measuring device (manufactured by BECKMAN COOLTER, product name: LS 13 320).
[Measurement condition]
Dispersion medium: Sodium hexametaphosphate aqueous solution Measurement upper limit: 2000 μm
Lower limit of measurement: 0.017 μm
Particle refractive index: 2.00
Particle shape: Non-spherical solvent Refractive index: 1.333
合成例
水酸化マグネシウム（ナカライテスク製）３０００ｇを２０Ｌのイオン交換水に添加し、撹拌して水酸化マグネシウムのスラリーを得た。
上記水酸化マグネシウムのスラリーを８０℃に加温し、ケイ酸ナトリウム（日本化学工業製）をＳｉＯ２として３００ｇ加えた後、更に、スラリーのｐＨが９になるまで、硫酸を１時間かけて加えた。このスラリーを８０℃で１時間熟成させ、水酸化マグネシウム粒子の表面に高密度のシリカ含有被覆層を形成した。得られたスラリーから被覆水酸化マグネシウム粒子を濾過にて分離、水洗し、乾燥し、粉砕して、本発明の塩素含有樹脂組成物の一成分であるアルカリ土類金属水酸化物を得た。 Synthesis Example 3000 g of magnesium hydroxide (manufactured by Nacalai Tesque) was added to 20 L of ion-exchanged water and stirred to obtain a magnesium hydroxide slurry.
The magnesium hydroxide slurry is heated to 80 ° C., 300 g of sodium silicate (manufactured by Nippon Chemical Industrial Co., Ltd.) is added as SiO 2 , and then sulfuric acid is further added over 1 hour until the pH of the slurry reaches 9. It was. This slurry was aged at 80 ° C. for 1 hour to form a high-density silica-containing coating layer on the surface of magnesium hydroxide particles. The coated magnesium hydroxide particles were separated from the obtained slurry by filtration, washed with water, dried, and pulverized to obtain an alkaline earth metal hydroxide which is a component of the chlorine-containing resin composition of the present invention.
１．原料
後述の表１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－７００、重合度７００ 1. 1. Raw Materials The raw materials listed in Table 1 below are as follows.
(A) Chlorine-containing resin Vinyl chloride resin: manufactured by Shin-Etsu Chemical Co., Ltd., TK-700, degree of polymerization 700
（ｂ）酸化亜鉛：堺化学工業社製、微細酸化亜鉛、平均粒子径０．２８μｍ (B) Zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd., fine zinc oxide, average particle size 0.28 μm
（ｃ）シリカ被覆水酸化マグネシウム：合成例に記載の水酸化マグネシウム粒子 (C) Silica-coated magnesium hydroxide: Magnesium hydroxide particles according to the synthetic example.
（ｄ）充填剤
重質炭酸カルシウム：白石カルシウム製　μパウダー３Ｓ (D) Filler Heavy calcium carbonate: μ powder 3S made of Shiraishi calcium
（ｅ）加工助剤
アクリル系加工助剤：カネカ製　カネエースＰＡ－２０ (E) Processing aid Acrylic processing aid: Kaneka Kaneka PA-20
（ｆ）安定剤
ステアリン酸亜鉛：堺化学工業社製、ＳＺ－Ｐ
ステアリン酸カルシウム：堺化学工業社製、ＳＣ－Ｐ (F) Stabilizer Zinc stearate: SZ-P manufactured by Sakai Chemical Industry Co., Ltd.
Calcium stearate: manufactured by Sakai Chemical Industry Co., Ltd., SCP
（ｇ）初着防止剤
ジベンゾイルメタン：油脂製品製、製品名　ＤＢＭ (G) Anti-first-attachment agent Dibenzoyl methane: Made of oil and fat products, product name DBM
（ｈ）耐熱助剤
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 (H) Heat-resistant aid dipentaerythritol: Dipentarit 300 manufactured by Koei Chemical Industry Co., Ltd.
実施例１～１２、比較例１～１２
塩化ビニル樹脂１００質量部に表１、２記載の添加剤を配合した。得られた塩化ビニル樹脂組成物をロール表面温度１７０℃に調整した８インチロール機（ＫＡＮＳＡＩ　ＲＯＬＬ社製）にて５分間混練し、厚さ０．３ｍｍのロールシートを作成した。このシートを用い、以下それぞれの試験を行った。結果を表１、２に示す。
＜プレス耐熱試験１＞
上記で作成したシートを７枚重ねてプレス表面温度２２０℃のプレス機（ＴＯＹＯＳＥＩＫＩ　ＭＩＮＩ　ＴＥＳＴ　ＰＲＥＳＳ－１０）を用い、厚さ２ｍｍになるように１００ｋｇ／ｃｍ２にて１分間保持した。プレス後のシートで、色差計にてＹＩ値を求めた。
ＹＩ値では耐熱性の差がわかりにくい場合もあるため、目視で黄変、褐変、黒変の変化の程度を判定し、同時にプレスシートに発生した気泡の多寡も判定した。耐熱性、発泡性は以下の基準で判定した。
［耐熱性］
◎：非常に良好（変色なし）
〇：良好（ほぼ変色なし）
×：不良（著しい変色あり）
［発泡性］
◎：気泡なし
〇：気泡数が３ｃｍ×３ｃｍ四方中１個以上１０個未満
×：気泡数が３ｃｍ×３ｃｍ四方中１０個以上
＜プレス耐熱試験２＞
上記で作成したシートを７枚重ねてプレス表面温度２２０℃のプレス機（ＴＯＹＯＳＥＩＫＩ　ＭＩＮＩ　ＴＥＳＴ　ＰＲＥＳＳ－１０）を用い、厚さ２ｍｍになるように１００ｋｇ／ｃｍ２にて５分間保持した。プレス後のシートで、プレス耐熱試験１と同様の評価を行った。 Examples 1-12, Comparative Examples 1-12
The additives shown in Tables 1 and 2 were added to 100 parts by mass of the vinyl chloride resin. The obtained vinyl chloride resin composition was kneaded with an 8-inch roll machine (manufactured by KANSAI ROLL) adjusted to a roll surface temperature of 170 ° C. for 5 minutes to prepare a roll sheet having a thickness of 0.3 mm. Using this sheet, each test was conducted below. The results are shown in Tables 1 and 2.
<Press heat resistance test 1>
Seven sheets prepared above were stacked and held at 100 kg / cm 2 for 1 minute using a press machine (TOYOSEIKI MINI TEST PRESS-10) having a press surface temperature of 220 ° C. to a thickness of 2 mm. The YI value was determined with a color difference meter on the sheet after pressing.
Since it may be difficult to see the difference in heat resistance from the YI value, the degree of change in yellowing, browning, and blackening was visually determined, and at the same time, the amount of bubbles generated on the press sheet was also determined. Heat resistance and foamability were judged according to the following criteria.
[Heat-resistant]
◎: Very good (no discoloration)
〇: Good (almost no discoloration)
×: Defective (with significant discoloration)
[Effervescent]
◎: No bubbles 〇: Number of bubbles is 1 or more and less than 10 in 3 cm × 3 cm square ×: Number of bubbles is 10 or more in 3 cm × 3 cm square <Press heat resistance test 2>
Seven sheets prepared above were stacked and held at 100 kg / cm 2 for 5 minutes using a press machine (TOYOSEIKI MINI TEST PRESS-10) having a press surface temperature of 220 ° C. to a thickness of 2 mm. The sheet after pressing was evaluated in the same manner as in the press heat resistance test 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表１、２に示した結果から、塩素含有樹脂組成物がシリカ被覆水酸化マグネシウム及び酸化亜鉛をそれぞれ所定の割合で含むことで、耐熱性に優れ、かつ、樹脂の発泡が抑制されることが確認された。シルバーストリークやフラッシュは樹脂の発泡を原因とするものであるため、この結果から、本発明の塩素含有樹脂組成物は、耐熱性に優れ、シルバーストリークやフラッシュの発生を十分に抑制することができる樹脂組成物であることが確認された。 From the results shown in Tables 1 and 2, it is possible that the chlorine-containing resin composition contains silica-coated magnesium hydroxide and zinc oxide in a predetermined ratio, respectively, to have excellent heat resistance and suppress the foaming of the resin. confirmed. Since silver streaks and flashes are caused by foaming of the resin, from this result, the chlorine-containing resin composition of the present invention has excellent heat resistance and can sufficiently suppress the generation of silver streaks and flashes. It was confirmed that it was a resin composition.

Claims (4)

  1. 塩素含有樹脂１００質量部に対して、シリカ被覆金属水酸化物として０．０７～０．９質量部のシリカ被覆水酸化マグネシウム及び／又はシリカ被覆水酸化カルシウムと、０．０２～０．３５質量部の平均粒子径が０．１～０．５μｍである酸化亜鉛とを含むことを特徴とする塩素含有樹脂組成物。 0.07 to 0.9 parts by mass of silica-coated magnesium hydroxide and / or silica-coated calcium hydroxide and 0.02 to 0.35 mass as silica-coated metal hydroxide with respect to 100 parts by mass of chlorine-containing resin. A chlorine-containing resin composition containing zinc oxide having an average particle size of 0.1 to 0.5 μm.
  2. 前記シリカ被覆金属水酸化物は、シリカ被覆水酸化マグネシウム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 silica-coated metal hydroxide is silica-coated magnesium hydroxide.
  3. 前記塩素含有樹脂組成物は、可塑剤の含有量が塩素含有樹脂１００質量部に対して、１質量部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。 The chlorine-containing resin composition according to claim 1 or 2, wherein the chlorine-containing resin composition has a plasticizer content of 1 part by mass or less with respect to 100 parts by mass of the chlorine-containing resin.
  4. 請求項１～３のいずれかに記載の塩素含有樹脂組成物を用いてなることを特徴とする成形体。 A molded product using the chlorine-containing resin composition according to any one of claims 1 to 3.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54114556A (en) * 1978-02-28 1979-09-06 Sakai Chem Ind Co Ltd Chlorine-containing resin composition
JPH05194809A (en) * 1992-01-20 1993-08-03 Mizusawa Ind Chem Ltd Flame retardant composition for chlorinated polymer, excellent in prevention of smoking, and its production
JP2001226548A (en) * 2000-02-15 2001-08-21 Fukuvi Chem Ind Co Ltd Chlorine-containing resin composition and chlorine- trapping agent composition
JP2006124502A (en) * 2004-10-28 2006-05-18 Sakai Chem Ind Co Ltd Stabilizer for halogen-containing resin, and halogen-containing resin composition
JP2006239026A (en) * 2005-03-01 2006-09-14 Terumo Corp Medical appliance composed of polyvinyl chloride resin
JP2010070681A (en) * 2008-09-19 2010-04-02 Sakai Chem Ind Co Ltd Chlorine-containing resin composition with suppressed foaming failure
JP2013136683A (en) * 2011-12-28 2013-07-11 Kuraray Co Ltd Chlorine atom containing resin composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54114556A (en) * 1978-02-28 1979-09-06 Sakai Chem Ind Co Ltd Chlorine-containing resin composition
JPH05194809A (en) * 1992-01-20 1993-08-03 Mizusawa Ind Chem Ltd Flame retardant composition for chlorinated polymer, excellent in prevention of smoking, and its production
JP2001226548A (en) * 2000-02-15 2001-08-21 Fukuvi Chem Ind Co Ltd Chlorine-containing resin composition and chlorine- trapping agent composition
JP2006124502A (en) * 2004-10-28 2006-05-18 Sakai Chem Ind Co Ltd Stabilizer for halogen-containing resin, and halogen-containing resin composition
JP2006239026A (en) * 2005-03-01 2006-09-14 Terumo Corp Medical appliance composed of polyvinyl chloride resin
JP2010070681A (en) * 2008-09-19 2010-04-02 Sakai Chem Ind Co Ltd Chlorine-containing resin composition with suppressed foaming failure
JP2013136683A (en) * 2011-12-28 2013-07-11 Kuraray Co Ltd Chlorine atom containing resin composition

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