WO2013035598A1

WO2013035598A1 - Thermoplastic resin composition for cleaning applications, and cleaning method

Info

Publication number: WO2013035598A1
Application number: PCT/JP2012/071814
Authority: WO
Inventors: 敬一造田; 茅野　義弘; 田原　久志; 中尾　公隆; 哈達鮑
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2011-09-06
Filing date: 2012-08-29
Publication date: 2013-03-14
Also published as: KR20140068932A; JP6115469B2; CN103781847B; CN103781847A; JPWO2013035598A1

Abstract

A thermoplastic resin composition for cleaning applications comprises (A) 30 to 90 parts by mass of a polycarbonate resin having a melt mass flow rate of 1 to 12 g/10 min. as measured under the conditions of a test temperature of 300ºC and a nominal load of 1.2 kg, (B) 5 to 70 parts by mass of an acrylonitrile-styrene copolymer having a melt mass flow rate of 4 to 10 g/10 min. as measured under the conditions of a test temperature of 220ºC and a nominal load of 10 kg, (C) 0.5 to 5 parts by mass of at least one lubricant, and (D) 5 to 40 parts by mass of at least one inorganic filler, and has a water content of 0.1 mass% or more.

Description

Thermoplastic resin composition for cleaning and cleaning method

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. Moreover, 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. When changing the thermoplastic resin to be used, it is necessary to clean the inside of 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.

The 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.

JP 05-0669446

By the way, when a 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, the above patent publication using a styrene resin as a main component When the inside of a molding cylinder or the like at a high temperature is cleaned using the cleaning thermoplastic resin composition disclosed in the publication, the viscosity of the cleaning thermoplastic resin composition is lowered and the shearing force is reduced. The detergency cannot be obtained. Further, since 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.

Accordingly, 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.

In order to achieve the above object, 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 (θ) 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 (θ) of 220 ° C. and 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 | or 0.4 mass% can be illustrated as an upper limit of a moisture content.

In the washing thermoplastic resin composition of the present invention, 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.

Further, in the thermoplastic resin composition for cleaning according to the present invention including the above preferred form, the composition ratio of acrylonitrile in the acrylonitrile-styrene copolymer is 25 mol% to 33 mol%. It is preferable from the viewpoint of reduction.

Further, in the thermoplastic resin composition for washing according to the present invention including the preferred embodiment described above, 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. At the start of cleaning, 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. Further, 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. Specifically, 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.

Examples of the starting aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5 -Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-5-nitrophenyl) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1 1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4 ′ -Dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxy-3-methylphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxy-3-methylphenyl) ethane and the like, preferably bis (4-hydroxyphenyl) alkanes And particularly preferably 2,2-bis (4-hydroxy). Phenyl) propane [referred to as bisphenol A]. These aromatic dihydroxy compounds can be used alone or in admixture of two or more.

In order to obtain a branched polycarbonate resin, 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%.

In the reaction by the interfacial polymerization method, in the presence of an organic solvent inert to the reaction, an alkaline aqueous solution, 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.

Here, 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. As a polymerization catalyst, 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. Usually, 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.

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. In the transesterification reaction using such raw materials, 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. In the transesterification method, it is preferable to use 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. Alternatively, 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.

If necessary, 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.

Here, examples of the antioxidant include organic phosphorus compounds such as phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, organic sulfur compounds, and phosphites. . Specifically, as a 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-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 And dimethyl ethyl} -2,4,8,10-spiro [5,5] undecane. Further, as hindered phenol antioxidants, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert. -Butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethyl Ethyl) -4-hydroxyphenyl] methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-ter -Butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert And -butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol.

As a heat stabilizer, 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). Specific examples of the phosphite compound (a) 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) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Examples thereof include phosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in combination of two or more.

Specific examples of 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. In these, an organic ultraviolet absorber is preferable. In particular, 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. Specific examples of benzotriazole compounds include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. . Specific examples of other 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 (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyle -Bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- And benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination. Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-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].

Examples of the light stabilizer include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, oxanilide-based UV absorbers, malonate-based UV absorbers, and hindered amines. Specific examples of 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 (α, α-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.

Examples of 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.

Examples of the lubricant 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. Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes an alicyclic carboxylic acid. Among these, preferable 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. As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, 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. Here, the aliphatic includes alicyclic compounds. Specific examples of 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. In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound. Specific examples of 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 α-olefin oligomer having 3 to 12 carbon atoms. Here, the alicyclic hydrocarbon is also included in the aliphatic hydrocarbon. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, 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. These 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.

Examples of the inorganic filler include calcium carbonate (CaCO ₂ ) and calcium silicate (CaSiO ₃ ). Alternatively, as an inorganic filler, glass fiber, carbon fiber, potassium titanate fiber, metal fiber, ceramic fiber, aramid fiber, PPS fiber, magnesium silicate, calcium sulfate, barium sulfate, titanium oxide, iron oxide, graphite, carbon black , Mica, asbestos, ceramic powder, metal flakes, plate glass, glass beads and the like, among which glass fiber, calcium silicate, magnesium silicate, mica, plate glass and glass beads are preferable, Glass fiber is preferred. Moreover, as an inorganic filler, what was surface-treated with a silane coupling agent, a titanium coupling agent, etc. is especially preferable. Examples of the surface treatment agent include γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyldimethoxymethylsilane, and the like. Epoxy silanes such as aminosilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, isopropyl tristearoyl titanate, isopropyltri Examples thereof include titanium coupling agents such as dodecylbenzenesulfonyl titanate and tetraisopropylbis (dioctyl phosphite) titanate.

As described above, 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. Examples of the injection molding machine (injection molding apparatus) include a known in-line screw type, plunger type, and screw / prepa type injection molding machine. As the extrusion 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. However, the structure, configuration, and type of the die are essentially arbitrary.

In the cleaning 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. Therefore, as a result of being able to achieve volume expansion of the cleaning thermoplastic resin composition without adding a chemical foaming agent, the thermoplastic resin remaining inside can be easily extruded from a molding cylinder or the like, In addition, 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. In addition, since 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. . In addition, since the lubricant is added, the 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. In addition, since 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.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples, and various numerical values and materials in the examples are examples.

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.

Moreover, in the cleaning method of 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. In Table 1, “AN / SAN ratio” means the composition ratio (unit: mol%) of acrylonitrile in the acrylonitrile-styrene copolymer, and “PE-WAX” means polyethylene wax. In 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. and a relative humidity of about 50%. The values shown in Table 1 were obtained based on the method of absorbing water up to the water absorption rate. As the polycarbonate resin, Iupilon E2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used, and as the acrylonitrile-styrene copolymer, Sanrex series manufactured by Techno Polymer Co., Ltd. was used.

Here, in Comparative Example 1A, polycarbonate resin is not used. On the other hand, Comparative Example 1B does not use an acrylonitrile-styrene copolymer. In Comparative Example 1C, 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. Further, in 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. and a nominal load of 10 kg. An acrylonitrile-styrene copolymer having a low viscosity of 25 grams / 10 minutes is used. Furthermore, in Comparative Example 1C, the composition ratio of acrylonitrile in the acrylonitrile-styrene copolymer is 35%. Moreover, in 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.

In an injection molding machine (Sodick Plustech Co., Ltd.), first, injection molding was performed using black PPE pellets (Iupiace AN60 (Black) manufactured by Mitsubishi Engineering Plastics Co., Ltd.). After that, as a detergency test, the injection molding was repeated using the washing thermoplastic resin composition, the inside of the molding cylinder was replaced with the washing thermoplastic resin composition, and the washing thermoplastic required until the black color disappeared sufficiently. The mass of the resin composition was measured. The results are shown in Table 1 as “cleanability” (unit: kilogram). In addition, after the detergency test, injection molding was repeated using a transparent polycarbonate resin (Iupilon E2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.), and the inside of the molding cylinder was replaced with a polycarbonate resin. The mass of the polycarbonate resin required until it was obtained was measured. The results are shown in Table 1 as “substitution” (unit: kilogram).

The cleaning thermoplastic resin compositions of 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.

[Table 1]

When the inside of the molding cylinder was washed using the washing thermoplastic resin composition of Example 1A and Comparative Example 1A, the torque of the screw disposed in the molding cylinder (screw torque value. Unit: kg · m 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.). In the cleaning, the amount of the thermoplastic resin composition for cleaning per unit time is the same in Example 1A and Comparative Example 1A. At the start of cleaning, the temperature of the cleaning thermoplastic resin composition of Example 1A and Comparative Example 1A of the molding cylinder was 280 ° C. In the cleaning thermoplastic resin composition of Example 1A, 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. This means that even if the temperature in the molding cylinder decreases, the 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 | cleaning of the heating cylinder with which the extruder was equipped.

Claims

(A) 30 to 90 parts by weight of a polycarbonate resin having a melt mass flow rate 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 weight to 70 parts by weight of an acrylonitrile-styrene copolymer having a melt mass flow rate 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;
(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
A cleaning thermoplastic resin composition having a water content of 0.1% by mass or more.
2. The thermoplastic resin composition for cleaning according to claim 1, wherein the polycarbonate resin has a weight average molecular weight of 2.2 × 10 4 to 3.2 × 10 4 .
The cleaning thermoplastic resin composition according to claim 1 or 2, wherein the composition ratio of acrylonitrile in the acrylonitrile-styrene copolymer is 25 mol% to 33 mol%.
The thermoplastic resin for washing according to any one of claims 1 to 3, wherein the acrylonitrile-styrene copolymer has a weight average molecular weight of 1.6 x 10 5 to 2.7 x 10 5 . Resin composition.
(A) 30 to 90 parts by weight of a polycarbonate resin having a melt mass flow rate 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 weight to 70 parts by weight of an acrylonitrile-styrene copolymer having a melt mass flow rate 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;
(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
Using a washing thermoplastic resin composition having a water content of 0.1% by mass or more, washing a molding cylinder provided in an injection molding machine or a heating cylinder provided in an extrusion molding machine A characteristic cleaning method.
6. The cleaning method according to claim 5, wherein the temperature of the cleaning thermoplastic resin composition in the molding cylinder or the heating cylinder is set to 240 ° C. to 300 ° C. at the start of cleaning.