WO2013111633A1 - 成形加工機洗浄用の熱可塑性樹脂組成物 - Google Patents

成形加工機洗浄用の熱可塑性樹脂組成物 Download PDF

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WO2013111633A1
WO2013111633A1 PCT/JP2013/050511 JP2013050511W WO2013111633A1 WO 2013111633 A1 WO2013111633 A1 WO 2013111633A1 JP 2013050511 W JP2013050511 W JP 2013050511W WO 2013111633 A1 WO2013111633 A1 WO 2013111633A1
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component
thermoplastic resin
molding machine
resin composition
resin
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PCT/JP2013/050511
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English (en)
French (fr)
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脇田直樹
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ダイセルポリマー株式会社
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Application filed by ダイセルポリマー株式会社 filed Critical ダイセルポリマー株式会社
Priority to EP13741298.7A priority Critical patent/EP2808149B1/en
Priority to US14/373,469 priority patent/US9144924B2/en
Priority to CN201380004146.7A priority patent/CN103958145B/zh
Priority to KR1020147015998A priority patent/KR101996923B1/ko
Publication of WO2013111633A1 publication Critical patent/WO2013111633A1/ja
Priority to IN5967DEN2014 priority patent/IN2014DN05967A/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/70—Maintenance
    • B29C33/72—Cleaning
    • B29C33/722—Compositions for cleaning moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/70—Maintenance
    • B29C33/72—Cleaning
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/757—Moulds, cores, dies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to a thermoplastic resin composition for washing a molding machine for washing molding machines such as an extruder and an injection molding machine.
  • thermoplastic resin molding machine As a cleaning agent for a thermoplastic resin molding machine, a combination of a base resin and other components is known.
  • JP 2010-95624 A JP 2010-95625 A, JP 2011-46808 A, JP 10-279816 A and JP 2007-21765 A
  • a base resin and an anionic surfactant are used.
  • a combined detergent composition is disclosed. Summary of the Invention
  • An object of the present invention is to provide a thermoplastic resin composition for cleaning a molding machine, in which the cleaning performance is further improved by combining a base resin and a surfactant.
  • the combination of the nonionic surfactant and the metal salt of the acidic phosphate ester further improves the cleaning performance and improves the workability.
  • the headline and the present invention were completed.
  • thermoplastic resin composition for washing a molding machine comprising (C) a nonionic surfactant and (D) a metal salt of an acidic phosphate.
  • This invention provides the use which uses the said thermoplastic resin composition for a shaping
  • the cleaning thermoplastic resin composition of the present invention has good cleaning properties and workability when cleaning the interior of thermoplastic resin molding and processing equipment such as extruders and injection molding equipment.
  • styrenic resin examples include PS resins (polystyrene homopolymers) and copolymers (however, they do not contain (meth) acrylic acid units).
  • copolymer examples include ABS (acrylonitrile-butadiene-styrene) resin, AS (acrylonitrile-styrene) resin, ASA (acrylonitrile-styrene-acrylic rubber) resin, AES (acrylonitrile-ethylenepropylene rubber-styrene) resin, ACS (acrylonitrile).
  • -Chlorinated polyethylene-styrene) resin HIPS resin (impact polystyrene), SB (styrene-butadiene) resin, SBS (styrene-butadiene-styrene) resin, SEBS resin (styrene-ethylene / butylene-styrene), SIS ( Examples thereof include those selected from styrene-isoprene-styrene resin, SIBS (styrene-isoprene / butadiene-styrene) resin, SEPS (styrene-ethylene / propylene-styrene) resin, and the like. It may be used in combination.
  • Resins containing (meth) acrylic acid ester units are MS (methyl methacrylate-styrene) resin, PMMA (polymethyl methacrylate) resin, maleic anhydride-styrene-MMA (methyl methacrylate) copolymer, MBS (methyl methacrylate-).
  • MS methyl methacrylate-styrene
  • PMMA polymethyl methacrylate
  • maleic anhydride-styrene-MMA methyl methacrylate copolymer
  • MBS methyl methacrylate-
  • examples thereof include those selected from butadiene-styrene) resins, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) resins, and the like, and these may be used in combination.
  • the component (A) may be a styrene resin alone or a mixture of a styrene resin and a resin containing a (meth) acrylic acid ester unit.
  • the content rate of a styrene-type resin is 60 mass% or more, and it is more preferable that it is 70 mass% or more.
  • the alkali metal salt of a fatty acid is preferably a Na, K, Li or Cs salt of a saturated or unsaturated fatty acid having 10 to 22 carbon atoms.
  • the fatty acid may be linear or branched.
  • Na salts of fatty acids having 12 to 18 carbon atoms lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid are more preferable.
  • the content ratio of the alkali metal salt of the fatty acid of the component (B) in the composition is 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, more preferably 100 parts by weight of the component (A). 1 to 5 parts by mass.
  • the nonionic surfactant (C) is an oxyethylene chain surfactant, a sorbitan ester surfactant, a glyceride (glycerin (mono, di) fatty acid ester) surfactant, 12-hydroxystearin.
  • a sorbitan ester surfactant examples thereof include those selected from acid esters, propylene glycol fatty acid esters, sucrose fatty acid esters, alkyl glyceryl ethers, alkyl glucosides, and the like.
  • at least one selected from sorbitan fatty acid ester, glycerin fatty acid ester, and 12-hydroxystearic acid ester is preferable.
  • the content of the nonionic surfactant as the component (C) in the composition is 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, more preferably 100 parts by weight of the component (A). 1 to 5 parts by mass.
  • the content of component (B) in the total amount of component (B) and component (C) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and the content of component (C) is the balance. is there.
  • a component is a metal salt of acidic phosphate ester.
  • the component (C) is decomposed by the action of the alkali metal contained in the component (B) and gas ((gas containing fatty acid etc.)). It is a component that acts to prevent the generation of
  • a salt of an acidic phosphate ester represented by the general formula (I) or (II) described in paragraph numbers 0021 to 0032 of JP2010-189515A can be used. it can.
  • magnesium stearyl acid phosphate, calcium stearyl acid phosphate, zinc stearyl acid phosphate, aluminum stearyl acid phosphate and the like are preferable.
  • commercially available products can be used. For example, zinc stearyl acid phosphate (LBT1830 manufactured by Sakai Chemical Industry Co., Ltd.), aluminum stearyl acid phosphate (LBT1813 manufactured by Sakai Chemical Industry Co., Ltd.), calcium stearyl acid. Phosphate (LBT1820 manufactured by Sakai Chemical Industry Co., Ltd.), magnesium stearyl acid phosphate (LBT-1812) and the like can be used.
  • the content ratio of the component (D) in the composition is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass is more preferable.
  • the composition of the present invention can further contain an inorganic filler.
  • the inorganic filler include well-known glass fibers and metal fibers, as well as those selected from molten slag, steel slag, crushed materials thereof, and artificial mineral fibers described in JP-A-2006-257297. And non-fibrous (powdered, granular, crushed, etc.) can be used.
  • composition of the present invention may further contain an alkylene glycol fatty acid ester, an organic phosphorus compound, a polyhydric alcohol, and a metal soap described in JP-A-2006-257297.
  • composition of the present invention is produced by premixing the above components with a mixer such as a Henschel mixer, a tumbler blender, or a kneader, and then kneading with an extruder, or melt-kneading with a heating roll or a Banbury mixer. To do.
  • a mixer such as a Henschel mixer, a tumbler blender, or a kneader
  • HIPS red-colored product (red pigment concentration: 0.5%) was injection-molded as a prior use resin. Thereafter, the measurement and injection operations were repeated using each composition shown in Table 1, and when the red color disappeared, the washing was finished, and the detergency was evaluated based on the amount (kg) of the composition used so far.
  • AS resin Cosmetic N 050SF manufactured by Daicel Polymer Co., Ltd.
  • the cleaning property depends on whether the resin used in advance (HIPS, which is the previous material) is red. evaluated.
  • A Component PS resin: Toyo Styrene Co., Ltd. Toyo Styrol GP MW1C PMMA resin: Mitsubishi Rayon Co., Ltd. Acripet MF MS resin: Daicel Polymer Co., Ltd. Sebian MAS30
  • B component Na stearate Component
  • Nonionic surfactant 1 Glycerin hydroxystearate
  • Nonionic surfactant 2 Sorbitan stearate
  • D Component Acidic phosphate ester salt: Zinc stearyl acid phosphate (LBT-1830 manufactured by Sakai Chemical Industry Co., Ltd.)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

　押出機、射出成形機器等の熱可塑性樹脂成形加工機器の内部を洗浄する際の洗浄性と作業性が良い成形加工機洗浄用の熱可塑性樹脂組成物の提供。（Ａ）スチレン系樹脂を含む熱可塑性樹脂、（Ｂ）脂肪酸のアルカリ金属塩、（Ｃ）ノニオン性界面活性剤及び（Ｄ）酸性リン酸エステルの金属塩を含有する成形加工機洗浄用の熱可塑性樹脂組成物。

Description

成形加工機洗浄用の熱可塑性樹脂組成物
　本発明は、押出機、射出成形機等の成形加工機を洗浄するための成形加工機洗浄用の熱可塑性樹脂組成物に関する。
背景技術
　熱可塑性樹脂の成形加工機用の洗浄剤として、ベース樹脂と他の成分を組み合わせたものが知られている。
　特開２０１０－９５６２４号公報、特開２０１０－９５６２５号公報、特開２０１１－４６８０８号公報、特開平１０－２７９８１６号公報および特開２００７－２１７６５号公報には、ベース樹脂とアニオン界面活性剤を組み合わせた洗浄剤組成物が開示されている。
発明の概要
　本発明は、ベース樹脂と界面活性剤を組み合わせることによって、より洗浄性能が高められた成形加工機洗浄用の熱可塑性樹脂組成物を提供することを課題とする。
　本発明は、ベース樹脂成分と界面活性剤を組み合わせる際、ノニオン界面活性剤を組み合わせ、さらに酸性リン酸エステルの金属塩を組み合わせることによって、洗浄性能がより高められ、作業性も向上されることを見出し、本発明を完成した。
　本発明は、
　（Ａ）スチレン系樹脂を含む熱可塑性樹脂、
　（Ｂ）脂肪酸のアルカリ金属塩、
　（Ｃ）ノニオン性界面活性剤及び
　（Ｄ）酸性リン酸エステルの金属塩
を含有する成形加工機洗浄用の熱可塑性樹脂組成物を提供する。
　本発明は、上記熱可塑性樹脂組成物を成形加工機洗浄に用いる用途を提供する。
発明の詳細な説明
　本発明の洗浄用の熱可塑性樹脂組成物によれば、押出機、射出成形機器等の熱可塑性樹脂成形加工機器の内部を洗浄する際の洗浄性と作業性が良い。
　＜（Ａ）成分＞
　スチレン系樹脂は、ＰＳ樹脂（ポリスチレンホモポリマー）のほか、共重合体（但し、（メタ）アクリル酸単位は含まない）を挙げることができる。
　共重合体としては、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、ＡＳ（アクリロニトリル－スチレン）樹脂、ＡＳＡ（アクリロニトリル－スチレン－アクリルゴム）樹脂、ＡＥＳ（アクリロニトリル－エチレンプロピレンゴム－スチレン）樹脂、ＡＣＳ（アクリロニトリル－塩素化ポリエチレン－スチレン）樹脂、ＨＩＰＳ樹脂（耐衝撃性ポリスチレン）、ＳＢ（スチレン－ブタジエン）樹脂、ＳＢＳ（スチレン－ブタジエン－スチレン）樹脂、ＳＥＢＳ樹脂（スチレン－エチレン／ブチレン－スチレン）、ＳＩＳ（スチレン－イソプレン－スチレン）樹脂、ＳＩＢＳ（スチレン－イソプレン／ブタジエン－スチレン）樹脂、ＳＥＰＳ（スチレン－エチレン／プロピレン－スチレン）樹脂等から選ばれるものを挙げることができ、これらを組み合わせて使用することもできる。
　（メタ）アクリル酸エステル単位を含む樹脂は、ＭＳ（メチルメタクリレート－スチレン）樹脂、ＰＭＭＡ（ポリメチルメタクリレート）樹脂、無水マレイン酸－スチレン－ＭＭＡ（メチルメタクリレート）の共重合体、ＭＢＳ（メチルメタクリレート－ブタジエン－スチレン）樹脂、ＭＡＢＳ（メチルメタクリレート－アクリロニトリル－ブタジエン－スチレン）樹脂等から選ばれるものを挙げることができ、これらを組み合わせて使用することもできる。
　（Ａ）成分は、スチレン系樹脂のみでもよいし、スチレン系樹脂と（メタ）アクリル酸エステル単位を含む樹脂との混合物でもよい。
　前記混合物にするときは、スチレン系樹脂の含有割合が６０質量％以上であることが好ましく、７０質量％以上であることがより好ましい。
　＜（Ｂ）成分＞
　（Ｂ）脂肪酸のアルカリ金属塩は、炭素数１０～２２の飽和又は不飽和脂肪酸のＮａ、Ｋ、Ｌｉ、Ｃｓ塩が好ましい。脂肪酸は直鎖でもよいし、分岐していてもよい。
　これらの中でも炭素数１２～１８の脂肪酸（ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸）のＮａ塩がより好ましい。
　組成物中における（Ｂ）成分の脂肪酸のアルカリ金属塩の含有割合は、（Ａ）成分１００質量部に対して０．５～１０質量部であり、好ましくは１～１０質量部、より好ましくは１～５質量部である。
　＜（Ｃ）成分＞
　（Ｃ）成分のノニオン性界面活性剤は、オキシエチレン鎖型界面活性剤、ソルビタンエステル型界面活性剤、グリセリセライド系（グリセリン（モノ、ジ）脂肪酸エステル類）界面活性剤、12－ヒドロキシステアリン酸エステル、プロピレングリコ－ル脂肪酸エステル、ショ糖脂肪酸エステル、アルキルグリセリルエ－テル、アルキルグルコシド等から選ばれるものを挙げることができる。
　これらの中でも、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、12－ヒドロキシステアリン酸エステルから選ばれる１種以上が好ましい。
　組成物中における（Ｃ）成分のノニオン性界面活性剤の含有割合は、（Ａ）成分１００質量部に対して０．５～１０質量部であり、好ましくは１～１０質量部、より好ましくは１～５質量部である。
　（Ｂ）成分と（Ｃ）成分の合計量中における（Ｂ）成分の含有割合は３０～７０質量％が好ましく、４０～６０質量％がより好ましく、（Ｃ）成分の含有割合は残部割合である。
　＜（Ｄ）成分＞
　（Ｄ）成分は、酸性リン酸エステルの金属塩である。（Ｄ）成分は、（Ｂ）成分と（Ｃ）成分を併用したとき、（Ｂ）成分に含まれるアルカリ金属の作用により（Ｃ）成分が分解されてガス（（脂肪酸等を含むガス））を発生させることを防止するように作用する成分である。
　（Ｄ）成分は、例えば特開２０１０－１８９５１５号公報の段落番号００２１～段落番号００３２に記載された一般式（I）又は（II）で表される酸性リン酸エステルの塩を使用することができる。
　（Ｄ）成分としては、マグネシウムステアリルアシッドホスフェート、カルシウムステアリルアシッドホスフェート、亜鉛ステアリルアシッドホスフェート、アルミニウムステアリルアシッドホスフェート等が好ましい。
　（Ｄ）成分としては市販品を使用することができ、例えば、亜鉛ステアリルアシッドホスフェート（堺化学工業（株）製ＬＢＴ１８３０）、アルミニウムステアリルアシッドホスフェート（堺化学工業（株）製ＬＢＴ１８１３）、カルシウムステアリルアシッドホスフェート（堺化学工業（株）製ＬＢＴ１８２０）、マグネシウムステアリルアシッドホスフェート（ＬＢＴ－１８１２）等を使用することができる。
　組成物中の（Ｄ）成分の含有割合は、（Ｂ）成分と（Ｃ）成分の合計量１００質量部に対して５～８０質量部が好ましく、１０～７０質量部がより好ましく、１５～６０質量部がさらに好ましい。
　＜その他の成分＞
　本発明の組成物は、さらに無機フィラーを含有することができる。無機フィラーとしては、周知のガラス繊維や金属繊維のほか、特開２００６－２５７２９７号公報に記載の溶融スラグ、鉄鋼スラグ又はこれらの破砕物、人造鉱物繊維から選ばれるものを挙げることができ、繊維状のもの、非繊維状のもの（粉末状、粒状、破砕物等）を用いることができる。
　本発明の組成物は、さらに特開２００６－２５７２９７号公報に記載のアルキレングリコール脂肪酸エステル、有機燐化合物、多価アルコール、金属石鹸を含有することができる。
　本発明の組成物は、上記各成分を、ヘンシェルミキサー、タンブラーブレンダー、ニーダー等の混合機で予備混合した後、押出機で混練したり、加熱ロール、バンバリーミキサーで溶融混練したりすることによって製造する。
実施例
　実施例及び比較例
　表１に示す組成の各成分をタンブラーブレンダーで混合後、押出機にて溶融混練し、ペレット状の樹脂組成物を得た。これらの組成物を使用し、下記の方法で洗浄試験を行った。結果を表１に示す。
　射出成形機（住友重機械工業社製「ＳＨ１００」；シリンダー温度２３０℃）に、先行使用樹脂としてＨＩＰＳの赤色着色品（赤色色素濃度０．５％）１ｋｇを射出成形した。
　その後、表１の各組成物を用いて計量と射出の操作を繰り返し、赤色が消えた時点を洗浄終了として、それまでの組成物の使用量(kg)により洗浄性を評価した。
　また洗浄終了後にＡＳ樹脂（ダイセルポリマー株式会社製のセビアンＮ ０５０ＳＦ）を流したときに先行使用樹脂（前材であるＨＩＰＳ）の赤色がでるかどうかで洗浄性（前材の残留の有無）を評価した。
Figure JPOXMLDOC01-appb-T000001
　（Ａ）成分
　ＰＳ樹脂：東洋スチレン株式会社　トーヨースチロールＧＰ　ＭＷ１Ｃ
　ＰＭＭＡ樹脂：三菱レイヨン株式会社　アクリペットＭＦ
　ＭＳ樹脂：ダイセルポリマー株式会社　セビアンＭＡＳ３０
　（Ｂ）成分
　ステアリン酸Ｎａ
　（Ｃ）成分
　ノニオン界面活性剤１：グリセリンヒドロキシステアレート
　ノニオン界面活性剤２：ソルビタンステアレート
　（Ｄ）成分
　酸性リン酸エステル塩：亜鉛ステアリルアシッドホスフェート（堺化学工業（株）製ＬＢＴ－１８３０）

Claims (7)

  1. 　（Ａ）スチレン系樹脂を含む熱可塑性樹脂、
    　（Ｂ）脂肪酸のアルカリ金属塩、
    　（Ｃ）ノニオン性界面活性剤及び
    　（Ｄ）酸性リン酸エステルの金属塩
    を含有する成形加工機洗浄用の熱可塑性樹脂組成物。
  2. 　（Ｂ）成分と（Ｃ）成分の合計量中における（Ｂ）成分の含有割合が３０～７０質量％、（Ｃ）成分の含有割合が７０～３０質量％であり、
    　（Ｄ）成分の含有割合が、（Ｂ）成分と（Ｃ）成分の合計量１００質量部に対して１０～１００質量部である、請求項１記載の成形加工機洗浄用の熱可塑性樹脂組成物。
  3. 　（Ｄ）成分の酸性リン酸エステル塩が、マグネシウムステアリルアシッドホスフェート、カルシウムステアリルアシッドホスフェート、亜鉛ステアリルアシッドホスフェート、アルミニウムステアリルアシッドホスフェートから選ばれるものである、請求項１又は２記載の成形加工機洗浄用の熱可塑性樹脂組成物。
  4. 　（Ｃ）成分のノニオン性界面活性剤が、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステルから選ばれる１種以上のものである、請求項１～３のいずれか１項記載の成形加工機洗浄用の熱可塑性樹脂組成物。
  5. 　（Ａ）スチレン系樹脂を含む熱可塑性樹脂が、スチレン系樹脂（但し、（メタ）アクリル酸単位は含まない）と（メタ）アクリル酸エステル単位を含む樹脂との混合物である、請求項１～４のいずれか１項記載の成形加工機洗浄用の熱可塑性樹脂組成物。
  6. 　（メタ）アクリル酸エステル単位を含む樹脂が、ＭＳ樹脂、ＰＭＭＡ樹脂、無水マレイン酸－スチレン－ＭＭＡの共重合体から選ばれる１種以上のものである、請求項１～５のいずれか１項記載の成形加工機洗浄用の熱可塑性樹脂組成物。
  7. 請求項１～５のいずれか１項記載の熱可塑性樹脂組成物を成形加工機洗浄に用いる用途。
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