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WO2013035598A1 - Composition de résine thermoplastique destinée à des applications de nettoyage et procédé de nettoyage - Google Patents

Composition de résine thermoplastique destinée à des applications de nettoyage et procédé de nettoyage Download PDF

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Publication number
WO2013035598A1
WO2013035598A1 PCT/JP2012/071814 JP2012071814W WO2013035598A1 WO 2013035598 A1 WO2013035598 A1 WO 2013035598A1 JP 2012071814 W JP2012071814 W JP 2012071814W WO 2013035598 A1 WO2013035598 A1 WO 2013035598A1
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WIPO (PCT)
Prior art keywords
cleaning
thermoplastic resin
parts
resin composition
mass
Prior art date
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Ceased
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PCT/JP2012/071814
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English (en)
Japanese (ja)
Inventor
敬一 造田
茅野　義弘
田原　久志
中尾　公隆
哈達 鮑
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Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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Filing date
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Priority to KR1020147006019A priority Critical patent/KR20140068932A/ko
Priority to JP2013532547A priority patent/JP6115469B2/ja
Priority to CN201280043348.8A priority patent/CN103781847B/zh
Publication of WO2013035598A1 publication Critical patent/WO2013035598A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/1753—Cleaning or purging, e.g. of the injection unit

Definitions

  • the present invention relates to a cleaning thermoplastic resin composition and a cleaning method.
  • An injection molding machine used in injection molding includes a molding cylinder (also called a heating cylinder or a barrel) for plasticizing and melting a raw material thermoplastic resin.
  • the extrusion molding machine used in extrusion molding has a die and includes a heating cylinder for plasticizing and melting the raw material thermoplastic resin.
  • the molding cylinder and heating cylinder hereinafter, these may be collectively referred to as “molding cylinder, etc.”.
  • a thermoplastic resin composition for cleaning is used.
  • thermoplastic resin composition for cleaning is required to have a high viscosity and expand in volume inside the molding cylinder and the like in order to extrude the thermoplastic resin remaining inside the molding cylinder and the like.
  • a cleaning thermoplastic resin composition satisfying such a requirement is known from, for example, Japanese Patent Laid-Open No. 05-069446, and a styrene resin is a main component and a chemical foaming agent is added.
  • thermoplastic resin such as engineering plastics used at a high temperature (for example, 240 ° C. or more) remains inside a molding cylinder or the like
  • a high temperature for example, 240 ° C. or more
  • the above patent publication using a styrene resin as a main component
  • the viscosity of the cleaning thermoplastic resin composition is lowered and the shearing force is reduced.
  • the detergency cannot be obtained.
  • the chemical foaming agent is added, not only the manufacturing cost of the cleaning thermoplastic resin composition is increased, but there is a possibility that problems such as generation of decomposition residue of the foaming agent and generation of harmful gas may occur.
  • an object of the present invention is to perform internal cleaning of a molding cylinder or the like at a high temperature, and further, a thermoplastic resin composition for cleaning without adding a foaming agent, and a molding provided in an injection molding machine.
  • Another object of the present invention is to provide a cleaning method for a heating cylinder provided in an extrusion machine or an extrusion molding machine.
  • the cleaning thermoplastic resin composition of the present invention comprises: (A) The value of the melt mass flow rate under the conditions of a test temperature ( ⁇ ) of 300 ° C. and a nominal load (M nom ) of 1.2 kilograms is 1 gram / 10 minutes to 12 grams / 10 minutes, preferably 2 grams / 10. 30 to 90 parts by weight, preferably 40 to 80 parts by weight, more preferably 50 parts by weight of polycarbonate resin having a weight of 9 to 9 grams / 10 minutes, more preferably 3 to 10 grams to 6 grams / 10 minutes. Parts by mass to 70 parts by mass, (B) The value of the melt mass flow rate at a test temperature ( ⁇ ) of 220 ° C.
  • a nominal load (M nom ) of 10 kilograms is 4 grams / 10 minutes to 10 grams / 10 minutes, preferably 5 grams / 10 minutes to
  • the acrylonitrile-styrene copolymer of 8 grams / 10 minutes is 5 to 70 parts by weight, preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, (C) 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight of one or more lubricants, and (D) 5 to 40 parts by mass of one or more inorganic fillers, Including The water content is 0.1% by mass or more.
  • the total of the parts by mass of the polycarbonate resin, acrylonitrile-styrene copolymer, lubricant, and inorganic filler is 100 parts by mass. Moreover, 0.1 mass% thru
  • the weight average molecular weight (M W ) of the polycarbonate resin is 2.2 ⁇ 10 4 to 3.2 ⁇ 10 4, which is a high viscosity when melted at a high temperature. It is preferable from the viewpoints of reducing the adhesion to metal.
  • the composition ratio of acrylonitrile in the acrylonitrile-styrene copolymer is 25 mol% to 33 mol%. It is preferable from the viewpoint of reduction.
  • the weight average molecular weight (M W ) of the acrylonitrile-styrene copolymer is 1.6 ⁇ 10 5 to 2.7 ⁇ 10 6. 5 is preferable from the viewpoint of reducing the adhesiveness to metal.
  • the cleaning method of the present invention for achieving the above object is a molding cylinder provided in an injection molding machine using the cleaning thermoplastic resin composition of the present invention including the preferred embodiment described above, or
  • the heating cylinder provided in the extruder is cleaned.
  • the temperature of the cleaning thermoplastic resin composition in the molding cylinder or heating cylinder is preferably 230 ° C. to 360 ° C., preferably 240 ° C. to 300 ° C.
  • the melt mass flow rate can be measured based on JIS K7210: 1999.
  • the moisture content can be determined based on the Karl Fischer moisture measurement method.
  • the weight average molecular weight (M W ) of the polycarbonate resin can be determined based on a method of measuring as a standard polystyrene conversion value by gel permeation chromatography (GPC method), or an acrylonitrile-styrene copolymer.
  • the composition ratio of acrylonitrile in can be determined based on 1H-NMR measurement method, and the weight average molecular weight (M W ) of acrylonitrile-styrene copolymer is standard polystyrene by gel permeation chromatography (GPC method). It can be determined based on a method of measuring as a converted value.
  • the polycarbonate resin may be in the form of pellets or flakes.
  • the cleaning thermoplastic resin composition of the present invention can be produced based on the above-mentioned blending ratio, for example, based on kneading with an extruder, and control of the moisture content of the cleaning thermoplastic resin composition of the present invention. There is no need to use a special method, for example, it may be left indoors.
  • the polycarbonate resin can be synthesized based on a known method, and examples thereof include various synthesis methods including an interfacial polymerization method, a pyridine method, a transesterification method, and a ring-opening polymerization method of a cyclic carbonate compound.
  • an aromatic dihydroxy compound or a small amount thereof and a small amount of a polyhydroxy compound, carbonyl chloride generally known as phosgene, or a carbonic acid diester represented by dimethyl carbonate or diphenyl carbonate, carbon monoxide or carbon dioxide
  • It is a polymer or copolymer of a linear or branched thermoplastic aromatic polycarbonate obtained by reacting with a carbonyl compound.
  • phloroglucin 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4- Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris
  • a polyhydroxy compound represented by (4-hydroxyphenyl) ethane or the like, or 3,3 bis (4-hydroxyaryl) oxindole ( isatin bisphenol), 5-chloruisatin bisphenol, 5,7-dichloroisatin Bisphenol, 5-bromoisatin bisphenol, etc. as part of the above-mentioned aromatic dihydroxy compounds It may be placed, the amount is preferably 0.01 to 10 mol%, preferably from 0.1 to 2 mol%.
  • the pH is usually kept at 10 or more, an aromatic dihydroxy compound and a molecular weight modifier (terminal terminator), if necessary
  • Polycarbonate resin by using an antioxidant for antioxidants of aromatic dihydroxy compounds and reacting with phosgene, followed by addition of a polymerization catalyst such as tertiary amine or quaternary ammonium salt and interfacial polymerization Can be obtained.
  • the addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction.
  • the reaction temperature is 0 to 35 ° C., and the reaction time is several minutes to several hours.
  • examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. be able to.
  • examples of the molecular weight regulator or terminal terminator include compounds having a monovalent phenolic hydroxyl group. Specific examples include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p -Tert-butylphenol, p-long chain alkyl-substituted phenol and the like.
  • tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Can be mentioned.
  • the reaction by the transesterification method is a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound.
  • the molecular weight and terminal hydroxyl group amount of the desired polycarbonate resin are determined by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of vacuum during the reaction.
  • the amount of terminal hydroxyl groups has a great influence on the thermal stability, hydrolysis stability, color tone and the like of the polycarbonate resin, and is preferably 1000 ppm or less, particularly preferably 700 ppm or less, in order to have practical physical properties. It is common to use an equimolar amount or more of a carbonic acid diester with respect to 1 mol of the aromatic dihydroxy compound, and it is preferably used in an amount of 1.01 to 1.30 mol.
  • a transesterification catalyst When synthesizing a polycarbonate resin by the transesterification method, a transesterification catalyst is usually used.
  • the transesterification catalyst is not particularly limited, but alkali metal compounds and / or alkaline earth metal compounds are mainly used, and supplementary basic boron compounds, basic phosphorus compounds, basic ammonium compounds, or amine-based catalysts It is also possible to use a basic compound such as a compound in combination.
  • the reaction is performed at a temperature of 100 to 320 ° C., and finally, a secondary reaction such as aromatic hydroxy compound is performed under a reduced pressure of 2.7 ⁇ 10 2 Pa ( 2 mmHg) or less.
  • the method of performing a melt polycondensation reaction, removing a product is mentioned.
  • the melt polycondensation can be carried out batchwise or continuously, but in the case of a polycarbonate resin suitable for use in the present invention, it is preferably carried out continuously from the viewpoint of stability and the like.
  • a compound that neutralizes the catalyst for example, a sulfur-containing acidic compound, or a derivative formed therefrom, as a catalyst deactivator in the polycarbonate resin. It is added in the range of 0.5 to 10 equivalents, preferably 1 to 5 equivalents with respect to the alkali metal, and is usually added in the range of 1 to 100 ppm, preferably 1 to 20 ppm with respect to the polycarbonate resin.
  • the polycarbonate resin flakes can be obtained, for example, by dropping a methylene chloride solution containing a polycarbonate resin in an interfacial polymerization method into warm water kept at 45 ° C. and evaporating and removing the solvent, or alternatively
  • the methylene chloride solution containing the polycarbonate resin in the polymerization method can be put into methanol, and the precipitated polymer can be obtained by filtration and drying.
  • the methylene chloride solution containing the polycarbonate resin in the interfacial polymerization method can be obtained. Is stirred and pulverized while being kept at 40 ° C. with stirring by a kneader, and then desolvated with hot water of 95 ° C. or higher.
  • the obtained polycarbonate resin is isolated based on a well-known method, and then, for example, a well-known strand-type cold cut method (a polycarbonate resin once melted is formed into a strand shape, cooled, and then formed into a predetermined shape) Of hot cut method in the air), hot cut method in the air hot cut method (a method in which the polycarbonate resin once melted is cut into pellets before being exposed to water in the air), hot cut method in water
  • Polycarbonate resin pellets can be obtained by a hot cut method (a method in which a polycarbonate resin once melted is cut in water and simultaneously cooled and pelletized).
  • the obtained polycarbonate resin pellets are preferably dried as needed based on a method such as drying using a hot air drying furnace, a vacuum drying furnace, or a dehumidifying drying furnace.
  • Polycarbonate resins include additives such as antioxidants, phenolic, phosphorus, and sulfur heat stabilizers; benzotriazole and benzophenone UV absorbers; carboxylates, polysiloxane compounds, paraffin wax (polyolefins) ), A release agent such as polycaprolactone; an antistatic agent or the like may be added.
  • examples of the antioxidant include organic phosphorus compounds such as phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, organic sulfur compounds, and phosphites.
  • organic phosphorus compounds such as phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, organic sulfur compounds, and phosphites.
  • phenolic antioxidant 2,6-di-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4, 4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-
  • hindered phenol antioxidants pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert.
  • phosphite compound (a), phosphorous acid (b) in which at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms And at least one selected from the group of tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c).
  • phosphite compound (a) examples include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4-di-).
  • tert-butylphenyl) phosphite tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, Distearyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phyto, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeryth
  • ultraviolet absorbers include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide.
  • organic ultraviolet absorber is preferable.
  • benzotriazole compounds 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- On], at least one selected from the group of [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.
  • benzotriazole compounds include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol.
  • benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2 -(3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3 , 5-Bis ( ⁇
  • 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].
  • the light stabilizer examples include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, oxanilide-based UV absorbers, malonate-based UV absorbers, and hindered amines.
  • the light stabilizer include, for example, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- ( 2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) ) Benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), p-phenylenebis (1,3-benzoxazin-4-one), [(4-methoxyphenyl) -methylene] -malonic acid dimethyl Luester etc. can be mentioned.
  • acrylonitrile-styrene copolymers that satisfy the above-mentioned regulations of melt mass flow rate and weight average molecular weight (M W ) include, for example, Sanrex series from Technopolymer Co., Ltd., Sebian-N series from Daicel Polymer Co., Ltd., Asahi Kasei. Examples include Slitac AS series manufactured by Chemicals Co., Ltd. and Litec A series manufactured by Nippon A & L Co., Ltd.
  • the lubricant examples include at least one compound selected from the group consisting of an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000, and a polysiloxane silicone oil. it can.
  • the aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid.
  • the aliphatic carboxylic acid includes an alicyclic carboxylic acid.
  • aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable.
  • Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipic acid, And azelaic acid.
  • the same one as the aliphatic carboxylic acid can be used.
  • examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable.
  • the aliphatic includes alicyclic compounds.
  • alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. be able to.
  • said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.
  • Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
  • the alicyclic hydrocarbon is also included in the aliphatic hydrocarbon.
  • these hydrocarbon compounds may be partially oxidized.
  • paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
  • the number average molecular weight is preferably 200 to 5,000.
  • aliphatic hydrocarbons may be a single substance or a mixture of components and various molecular weights as long as the main component is within the above range.
  • examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.
  • the inorganic filler examples include calcium carbonate (CaCO 2 ) and calcium silicate (CaSiO 3 ).
  • glass fiber is preferred.
  • what was surface-treated with a silane coupling agent, a titanium coupling agent, etc. is especially preferable.
  • Examples of the surface treatment agent include ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyldimethoxymethylsilane, and the like.
  • Epoxy silanes such as aminosilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, isopropyl tristearoyl titanate, isopropyltri
  • titanium coupling agents such as dodecylbenzenesulfonyl titanate and tetraisopropylbis (dioctyl phosphite) titanate.
  • the cleaning thermoplastic resin composition of the present invention is used in the cleaning method of the present invention. That is, the cleaning thermoplastic resin composition of the present invention is provided in an injection molding machine used in injection molding, and is used for cleaning a molding cylinder (heating cylinder, barrel) for plasticizing and melting a raw thermoplastic resin. Alternatively, it can be used for washing a heating cylinder for plasticizing and melting a raw thermoplastic resin provided in an extruder used in extrusion molding, having a die.
  • the injection molding machine injection molding apparatus
  • injection molding apparatus include a known in-line screw type, plunger type, and screw / prepa type injection molding machine.
  • a well-known single-screw extruder including a vent-type extruder and a tandem-type extruder, and a well-known twin-screw extruder including a parallel twin-screw extruder and a conical twin-screw extruder can be used.
  • the structure, configuration, and type of the die are essentially arbitrary.
  • thermoplastic resin composition of the present invention a high viscosity polycarbonate resin having a melt mass flow rate value of 1 gram / 10 minutes to 12 grams / 10 minutes is used. Even when it is subjected to internal cleaning, etc., there is no problem that the viscosity decreases and shear force decreases, and the thermoplastic resin remaining inside the molding cylinder etc. can be reliably extruded, and sufficient cleaning power Can be obtained. Further, since the moisture content is 0.1% by mass or more, when the inside of the molding cylinder or the like is subjected to internal cleaning, the moisture in the cleaning thermoplastic resin composition becomes steam.
  • thermoplastic resin remaining inside can be easily extruded from a molding cylinder or the like,
  • the production cost of the cleaning thermoplastic resin composition is not increased, and problems such as generation of decomposition residues of the foaming agent and generation of harmful gases are not caused.
  • an acrylonitrile-styrene copolymer having a predetermined melt mass flow rate value is added, it has an excellent effect that it can be easily removed without sticking to metal parts such as screws and cylinders. .
  • thermoplastic resin remaining inside the molding cylinder or the like is easily peeled off from components (for example, screws) of the molding cylinder or the like, or is easily floated.
  • the inorganic filler is added, the thermoplastic resin remaining inside the molding cylinder or the like can be surely scraped off from components (for example, screws) such as the molding cylinder.
  • FIG. 1 is a graph showing the results of examining how the torque of a screw disposed in a molding cylinder changes from the start of cleaning using a lab plast mill (M model manufactured by Toyo Seiki Co., Ltd.). It is.
  • Example 1 relates to the cleaning thermoplastic resin composition and the cleaning method of the present invention.
  • the cleaning thermoplastic resin composition of Example 1 is (A) 30 to 90 parts by mass of a polycarbonate resin having a melt mass flow rate (MFR) value of 1 gram / 10 minutes to 12 grams / 10 minutes under the conditions of a test temperature of 300 ° C. and a nominal load of 1.2 kilograms. , (B) 5 parts by mass to 70 parts by weight of an acrylonitrile-styrene copolymer having a melt mass flow rate (MFR) value of 4 grams / 10 minutes to 10 grams / 10 minutes at a test temperature of 220 ° C. and a nominal load of 10 kilograms. Parts by mass, (C) 0.5 to 5 parts by mass of one or more lubricants, and (D) 5 to 40 parts by mass of one or more inorganic fillers, Including The water content is 0.1% by mass or more.
  • MFR melt mass flow rate
  • Example 1 using the cleaning thermoplastic resin composition of Example 1, a molding cylinder provided in an injection molding machine or a heating cylinder provided in an extrusion molding machine Perform cleaning.
  • Table 1 shows specific compositions of the cleaning thermoplastic resin compositions of Example 1A and Example 1B.
  • Table 1 shows specific compositions of the cleaning thermoplastic resin compositions of Comparative Example 1A, Comparative Example 1B, Comparative Example 1C, Comparative Example 1D, and Comparative Example 1E.
  • AN / SAN ratio means the composition ratio (unit: mol%) of acrylonitrile in the acrylonitrile-styrene copolymer
  • PE-WAX means polyethylene wax.
  • Example 1A, Example 1B, Comparative Example 1A, Comparative Example 1B, Comparative Example 1C, and Comparative Example 1D the moisture content was allowed to stand for 24 hours or more in an environment of a temperature of about 23 ° C.
  • Comparative Example 1A polycarbonate resin is not used.
  • Comparative Example 1B does not use an acrylonitrile-styrene copolymer.
  • the polycarbonate resin has a low viscosity viscosity with a melt mass flow rate (MFR) value of 28 grams / 10 minutes under the conditions of a polycarbonate resin test temperature of 300 ° C. and a nominal load of 1.2 kilograms. Is used.
  • MFR melt mass flow rate
  • Comparative Example 1C and Comparative Example 1D the acrylonitrile-styrene copolymer has a melt mass flow rate (MFR) value of 16 g / 10 min at a test temperature of 220 ° C.
  • Comparative Example 1C the composition ratio of acrylonitrile in the acrylonitrile-styrene copolymer is 35%.
  • Comparative Example 1E the cleaning thermoplastic resin composition is sufficiently dried to have a moisture content of 0.02% by mass.
  • the following method was carried out as a cleaning effect test.
  • Example 1A and Example 1B were cleaned more than any of the cleaning thermoplastic resin compositions of Comparative Example 1A, Comparative Example 1B, Comparative Example 1C, Comparative Example 1D, and Comparative Example 1E. The results showed excellent properties and substitution.
  • FIG. 1 shows the results of examining how) changes from the start of washing using a lab plast mill (M model manufactured by Toyo Seiki Co., Ltd.).
  • the amount of the thermoplastic resin composition for cleaning per unit time is the same in Example 1A and Comparative Example 1A.
  • the temperature of the cleaning thermoplastic resin composition of Example 1A and Comparative Example 1A of the molding cylinder was 280 ° C.
  • the screw torque showed a higher value at the start of cleaning than in Comparative Example 1A. This is because the cleaning thermoplastic resin composition of Example 1A has a high viscosity at the start of cleaning (that is, there is no problem that the viscosity is lowered and the shearing force is reduced) This suggests that it is thoroughly washed. On the other hand, when a certain amount of cleaning time had elapsed, the cleaning thermoplastic resin composition of Example 1A had the same screw torque value as that of the cleaning thermoplastic resin composition of Comparative Example 1A.
  • thermoplastic resin composition for cleaning tends to cause the thermoplastic resin remaining in the molding cylinder to be peeled off from the inner wall and screw of the molding cylinder, or Moreover, it becomes easy to float, and suggests that the thermoplastic resin remaining inside the molding cylinder is surely scraped off from the inner wall and screw of the molding cylinder. In addition, the same result was obtained also in washing

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine thermoplastique destinée à des applications de nettoyage comprenant (A) 30 à 90 parties en masse d'une résine polycarbonate présentant un indice de fluidité à chaud de 1 à 12 g/10 min tel que mesuré dans les conditions de température de test de 300ºC et sous une charge nominale de 1,2 kg, (B) 5 à 70 parties en masse d'un copolymère d'acrylonitrile-styrène présentant un indice de fluidité à chaud de 4 à 10 g/10 min tel que mesuré dans les conditions de température de test de 220ºC et sous une charge nominale de 10 kg, (C) 0,5 à 5 parties en masse d'au moins un lubrifiant et (D) 5 à 40 parties en masse d'au moins une charge inorganique et présentant une teneur en eau de 0,1% en masse ou plus.
PCT/JP2012/071814 2011-09-06 2012-08-29 Composition de résine thermoplastique destinée à des applications de nettoyage et procédé de nettoyage Ceased WO2013035598A1 (fr)

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KR1020147006019A KR20140068932A (ko) 2011-09-06 2012-08-29 세정용 열가소성 수지 조성물 및 세정 방법
JP2013532547A JP6115469B2 (ja) 2011-09-06 2012-08-29 洗浄用熱可塑性樹脂組成物及び洗浄方法
CN201280043348.8A CN103781847B (zh) 2011-09-06 2012-08-29 清洗用热塑性树脂组合物和清洗方法

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CN104858183A (zh) * 2015-05-11 2015-08-26 昆山恒光塑料制品有限公司 螺杆表层塑胶清理工艺
JP2017179213A (ja) * 2016-03-31 2017-10-05 株式会社東京商会 成形機及び押出機洗浄用樹脂組成物
KR102208535B1 (ko) * 2019-11-08 2021-01-28 우한기 냉난방기용 다층구조 알루미늄 배관의 제조방법 및 이에 의해 제조된 다층구조의 알루미늄 배관

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CN108219417B (zh) * 2016-12-15 2019-08-13 金发科技股份有限公司 一种pc/abs组合物及其制备方法和应用

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JP2009107160A (ja) * 2007-10-29 2009-05-21 Asahi Kasei Chemicals Corp 成形機用洗浄剤組成物
WO2011024828A1 (fr) * 2009-08-26 2011-03-03 ダイセルポリマー株式会社 Composition de résine thermoplastique pour le nettoyage

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JPH01167354A (ja) * 1987-12-24 1989-07-03 Asahi Chem Ind Co Ltd 成形機用洗浄剤
JPH0425600A (ja) * 1990-05-21 1992-01-29 Asahi Chem Ind Co Ltd 成形機用洗浄剤
JPH04183798A (ja) * 1990-11-20 1992-06-30 Asahi Chem Ind Co Ltd 成形機用洗浄剤
JPH0542547A (ja) * 1990-11-20 1993-02-23 Asahi Chem Ind Co Ltd 成形機用洗浄剤
JP2009107160A (ja) * 2007-10-29 2009-05-21 Asahi Kasei Chemicals Corp 成形機用洗浄剤組成物
WO2011024828A1 (fr) * 2009-08-26 2011-03-03 ダイセルポリマー株式会社 Composition de résine thermoplastique pour le nettoyage

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104858183A (zh) * 2015-05-11 2015-08-26 昆山恒光塑料制品有限公司 螺杆表层塑胶清理工艺
JP2017179213A (ja) * 2016-03-31 2017-10-05 株式会社東京商会 成形機及び押出機洗浄用樹脂組成物
KR102208535B1 (ko) * 2019-11-08 2021-01-28 우한기 냉난방기용 다층구조 알루미늄 배관의 제조방법 및 이에 의해 제조된 다층구조의 알루미늄 배관

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JPWO2013035598A1 (ja) 2015-03-23
JP6115469B2 (ja) 2017-04-19
KR20140068932A (ko) 2014-06-09
CN103781847B (zh) 2015-09-02

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