WO2021225168A1 - 成形機用洗浄剤 - Google Patents
成形機用洗浄剤 Download PDFInfo
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- WO2021225168A1 WO2021225168A1 PCT/JP2021/017561 JP2021017561W WO2021225168A1 WO 2021225168 A1 WO2021225168 A1 WO 2021225168A1 JP 2021017561 W JP2021017561 W JP 2021017561W WO 2021225168 A1 WO2021225168 A1 WO 2021225168A1
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- Prior art keywords
- cleaning agent
- resin
- molding
- viscosity
- copolymer
- Prior art date
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- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- UETLMBWMVIQIGU-UHFFFAOYSA-N calcium azide Chemical compound [Ca+2].[N-]=[N+]=[N-].[N-]=[N+]=[N-] UETLMBWMVIQIGU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 238000005194 fractionation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 201000002062 intestinal hypomagnesemia 1 Diseases 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005679 linear ultra low density polyethylene Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000003499 redwood Nutrition 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/802—Constructions or methods for cleaning the mixing or kneading device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/27—Cleaning; Purging; Avoiding contamination
- B29C48/2715—Cleaning; Purging; Avoiding contamination of plasticising units
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/27—Cleaning; Purging; Avoiding contamination
- B29C48/272—Cleaning; Purging; Avoiding contamination of dies
-
- 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
-
- 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
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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 cleaning agent for a resin molding machine.
- a resin molding machine such as an extrusion molding machine or an injection molding machine is used for operations such as coloring, mixing, and molding of a resin.
- the resin itself is obtained at the end of a predetermined operation.
- additives such as dyes and pigments contained in the molding material, deteriorated products (thermal decomposition products, charred products, charcoal products, etc.) generated from resins and the like may remain in the molding machine. If this residue is left unattended, the residue may be mixed into the molded product during the subsequent molding process of the resin, which may cause a poor appearance of the product.
- Patent Document 1 describes a method of increasing detergency by blending a nonionic surfactant with an olefin-based resin
- Patent Document 2 describes a method of enhancing detergency by blending an anionic surfactant with an olefin-based resin.
- Patent Document 3 describes a method of enhancing the detergency by blending an acid-modified product (styrene-maleic acid copolymer) with a thermoplastic resin.
- Patent Document 4 describes a method of enhancing the detergency by blending a methyl methacrylate-styrene copolymer with a thermoplastic resin.
- Patent Document 5 describes a method of enhancing the detergency by blending an inorganic filler with a thermoplastic resin.
- Patent Document 6 describes a method of enhancing the detergency by blending an alkali metal salt and / or an alkaline earth metal salt with a hydrocarbon-based resin.
- Patent Document 7 describes a method of enhancing the detergency by blending an inorganic filler with a thermoplastic resin.
- Patent Document 8 describes a method in which a concentrated sprayable composition containing a surfactant and an antimist component does not generate an aerosol of small particles.
- Patent Document 9 describes a method of enhancing the detergency by blending a surfactant and an inorganic filler with a thermoplastic resin.
- Patent Document 10 describes a method of improving detergency and replaceability by blending an inorganic foaming agent with a thermoplastic resin.
- the cleaning agent described in Patent Document 8 relates to a sprayable aqueous composition, and has a problem that it is unsuitable for resin replacement of a resin molding processing machine.
- the cleaning agent described in Patent Document 9 has been confirmed to have an effect of improving cleaning performance by blending an inorganic salt or metal hydroxide and an inorganic filler, the amount and time of resin for replacing the cleaning agent with a molding material There was a problem that it took. Even when the inorganic foaming agent described in Patent Document 10 is blended, the cleaning performance is insufficient, and there is a problem that the amount of resin and the time required for replacing the cleaning agent with the molding material are long.
- the cleaning agent is required to have high detergency for the molding material used in the previous molding and easy replacement with the molding material used for the next molding.
- an object of the present invention is to provide a cleaning agent for a resin molding machine having an improved balance between cleaning performance and ease of replacement by a molding material after cleaning.
- the present inventors have focused on the rheological properties of the thermoplastic resin so that the cleaning agent can be easily replaced in the molding machine, and have a specific branching index.
- the present invention has been developed by finding that the cleaning agent can be easily replaced without staying in the molding machine even when the flow path inside the mold or die for extrusion molding or injection molding is complicated. ..
- a cleaning agent for a molding machine which comprises a thermoplastic resin having a long-chain branched structure and has a branching index of more than 0.30 and less than 1.00 at an absolute molecular weight of 1,000,000.
- the extensional viscosity of 190 ° C. at a shear rate of 100 sec -1, proportion of shear viscosity of 190 ° C. at a shear rate of 100 sec -1 (elongational viscosity / shear viscosity) is 30 or more, the molding machine cleaning agent according to [1] .. [3] [1] or [2], wherein the extensional viscosity at 190 ° C.
- the cleaning agent for molding machines [4] The cleaning agent for a molding machine according to any one of [1] to [3], which contains 5% by mass or more and 70% by mass or less of the thermoplastic resin having the long-chain branched structure. [5] The cleaning agent for a molding machine according to any one of [1] to [4], wherein the storage elastic modulus at 190 ° C. at an angular velocity of 100 rad / sec is 80 kPa or more.
- the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
- the present invention is not limited to the following embodiment, and can be modified in various ways within the scope of the gist thereof.
- the detergent for molding machines of the present embodiment (in this specification, may be simply referred to as “detergent” or “detergent composition”) contains a thermoplastic resin having a long-chain branched structure and has an absolute molecular weight.
- the branch index at 1 million is greater than 0.30 and less than 1.00.
- the cleaning agent may further contain additives such as lubricants and surfactants.
- the thermoplastic resin contained in the cleaning agent for a molding machine of the present embodiment includes a thermoplastic resin having a long-chain branched structure. It may be composed of only a thermoplastic resin having a long-chain branched structure, or may be a mixture of a thermoplastic resin having a long-chain branched structure and a thermoplastic resin having no long-chain branched structure.
- the long chain branch structure is a branch having a length comparable to that of the main chain, while the short chain branch means a branch having a length of up to several carbon atoms.
- thermoplastic resin having a long-chain branched structure In order to achieve high detergency and easy replacement in the cleaning agent for molding machines of the present embodiment, it is important to include a thermoplastic resin having a long-chain branched structure, and by having a long-chain branched structure, The molding material used in the previous molding can be easily switched to the cleaning agent.
- the reason why the above effect is achieved is not always clear, but it is considered as follows. That is, the flow of the conventional cleaning agent is controlled by the shear flow, and the molding material and the cleaning agent tend to stay in the dead space inside the die. It is considered that material replacement can be promoted by expressing a circulating flow like a vortex by the flow.
- the cleaning agent for a molding machine of the present embodiment is preliminarily containing a thermoplastic resin having a long-chain branched structure, or is long in a thermoplastic resin having no long-chain branched structure.
- the thermoplastic resin having the long chain branching structure is contained.
- the method for introducing the long-chain branched structure into the thermoplastic resin is not particularly limited, and a conventionally known method can be used for each thermoplastic resin.
- the branching index can be mentioned as a direct index that the thermoplastic resin has a long chain branching.
- a polymer molecular chain having a branched structure introduced has an inertia as compared with a linear polymer molecular chain. Since the radius becomes smaller and the ultimate viscosity becomes smaller accordingly, the ratio of the ultimate viscosity ([ ⁇ ] br) of the branched polymer to the ultimate viscosity ([ ⁇ ] lin) of the linear polymer as the branched structure is introduced. It is known that the branching index represented by ([ ⁇ ] br / [ ⁇ ] lin) becomes smaller.
- the branching index represented by the ratio of the ultimate viscosity [ ⁇ ] br of the polymer to the ultimate viscosity [ ⁇ ] lin of the linear polymer at an absolute molecular weight of 1 million ([ ⁇ ] br / [ ⁇ ] lin) is less than 1.
- it means that it has a branched structure.
- Mark-Houwink-lot that the logarithm of [ ⁇ ] lin of a linear polymer has a linear relationship with the logarithm of molecular weight.
- thermoplastic resin examples include a branched polymer, a comb-shaped polymer, a star-shaped polymer, a network polymer structure, and the like in addition to the long-chain branching.
- a plastic resin can also be preferably used.
- thermoplastic resin contained in the cleaning agent for a molding machine of the present embodiment a thermoplastic resin used for general injection molding, extrusion molding, etc. can be widely used, and one type may be used alone or two or more types may be used. It can also be used in combination.
- thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer resin, an ethylene-aliphatic unsaturated carboxylic acid copolymer resin such as an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, and the like.
- Ethylene-aliphatic carboxylic acid ester copolymer resin ionomer resin, styrene resin such as polystyrene, polycarbonate resin, polyamide resin, polyester resin, polyvinyl chloride resin and the like are preferable.
- the content of the thermoplastic resin is preferably 50.0 to 99.9% by mass, preferably 60.0 to 99% by mass, based on 100% by mass of the cleaning agent composition, from the viewpoint of detergency and easy replacement. It is more preferably 9% by mass, and even more preferably 70.0 to 99.9% by mass.
- the polyolefin-based resin a polyethylene-based resin, a polypropylene-based resin, and a polybutene-based resin are preferable.
- the polyethylene-based resin refers to a homopolymer of ethylene or a copolymer of ethylene and one or more other types of monomers and having an ethylene content of 50% by mass or more. ..
- the polypropylene-based resin is a homopolymer of propylene or a copolymer of propylene and one or more other monomers, and has a propylene content of 50% by mass or more.
- the polybutene-based resin is a homopolymer of butene or a copolymer of butene and one or more other monomers, and has a butene content of 50% by mass or more.
- polyethylene-based resin examples include polyethylene and an ethylene- ⁇ -olefin copolymer. Specifically, high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and the like. Examples thereof include linear ultra-low density polyethylene (VLDPE, ULDPE) and ultra-high molecular weight polyethylene (UHMWPE).
- HDPE high-density polyethylene
- LDPE low-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE linear ultra-low density polyethylene
- ULDPE ultra-high molecular weight polyethylene
- the ethylene- ⁇ -olefin copolymer is preferably a copolymer composed of ethylene and at least one selected from ⁇ -olefins having 3 to 20 carbon atoms, and has ethylene and 3 to 12 carbon atoms. More preferably, it is a copolymer composed of at least one selected from ⁇ -olefins.
- the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-decene, 1-decene.
- Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosane and the like can be mentioned, and one or more of these can be used in combination.
- ethylene- ⁇ -olefin copolymer a copolymer of ethylene and at least one comonomer selected from a propylene comonomer, a butenko monomer, a hexenko monomer and an octene comonomer is generally easily available. Can be suitably used.
- the polyethylene-based resin can be polymerized using a known catalyst such as a chromium-based catalyst, a Ziegler-based catalyst, or a metallocene-based catalyst, and from the viewpoint of cleaning performance, a chromium-based catalyst or a Ziegler-based catalyst having a wide molecular weight distribution can be used.
- a chromium-based catalyst having a long-chain branch of a molecular chain having 6 or more carbon atoms or a metallocene catalyst is more preferable.
- the polyethylene-based resin may be used alone or in combination of two or more. From the viewpoint of cleaning performance, a polyethylene-based resin having a long-chain branched structure is more preferable.
- the polyethylene resin preferably has an MFR (190 ° C., load 2.16 kg) of 0.01 to 30 g / 10 min, and more preferably 0.05 to 25 g / 10 min. It is preferably 0.1 to 20 g / 10 min, and more preferably 0.1 to 20 g / 10 min.
- polypropylene-based resin examples include polypropylene, a propylene- ⁇ -olefin copolymer, and a ternary copolymer of propylene, ethylene, and ⁇ -olefin.
- the propylene- ⁇ -olefin copolymer is a copolymer composed of at least one selected from propylene and ⁇ -olefin.
- the propylene- ⁇ -olefin copolymer is preferably a copolymer composed of propylene and at least one selected from ethylene and an ⁇ -olefin having 4 to 20 carbon atoms, and is preferably propylene, ethylene and 4 to 8 carbon atoms.
- a copolymer composed of at least one selected from the ⁇ -olefins of the above is more preferable.
- examples of the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like.
- examples thereof include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosane, etc., and one or more of these can be used in combination.
- These copolymers may be in any form such as a block copolymer and a random copolymer, and are preferably a random copolymer of propylene and ethylene.
- propylene- ⁇ -olefin copolymer a copolymer of propylene and at least one comonomer selected from ethylene comonomer, butenko monomer, hexenko monomer and octene comonomer is generally easily available and is preferable. Can be used.
- ternary copolymer of propylene, ethylene and ⁇ -olefin a ternary copolymer of propylene, ethylene and ⁇ -olefin such as butene, hexene and octene can be preferably used.
- ternary copolymers may be in any form such as a block copolymer and a random copolymer, and are preferably a random copolymer of propylene, ethylene and butene.
- the polypropylene-based resin may be not only a resin polymerized with a catalyst such as a Ziegler-Natta catalyst, but also a resin polymerized using a known catalyst such as a metallocene-based catalyst.
- a catalyst such as a Ziegler-Natta catalyst
- a metallocene-based catalyst for example, syndiotactic polypropylene or iso Tactic polypropylene and the like can also be used.
- the polypropylene-based resin preferably has a long-chain branch from the viewpoint of cleaning performance, and for example, the branch can be introduced by grafting or polymerization by ionizing radiation irradiation.
- the polypropylene resin preferably has an MFR (230 ° C., load of 2.16 kg) of 0.01 to 30.0 g / 10 min, and more preferably 0.05 to 25 g / 10 min. It is preferably 0.1 to 20 g / 10 min, and more preferably 0.1 to 20 g / 10 min.
- the polybutene-based resin has particularly excellent compatibility with the polypropylene-based resin, it is preferable to use the polybutene-based resin in combination with the polypropylene-based resin for the purpose of adjusting the melt viscosity.
- the polybutene-based resin a copolymer consisting of butene and at least one selected from ethylene, propylene and an olefin-based compound having 5 to 8 carbon atoms, which is crystalline, can be preferably used.
- the ethylene-vinyl acetate copolymer resin refers to a copolymer obtained by copolymerizing an ethylene monomer and a vinyl acetate monomer.
- the ethylene-aliphatic unsaturated carboxylic acid copolymer resin refers to a copolymer obtained by copolymerizing an ethylene monomer and at least one monomer selected from an aliphatic unsaturated carboxylic acid. Examples of the aliphatic unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like.
- the ethylene-aliphatic unsaturated carboxylic acid ester copolymer resin refers to a copolymer obtained by copolymerizing an ethylene monomer and at least one monomer selected from an aliphatic unsaturated carboxylic acid ester.
- the aliphatic unsaturated carboxylic acid ester include acrylic acid ester, methacrylic acid ester, fumaric acid ester, maleic acid ester and the like.
- the copolymerization of the above-mentioned copolymer resin can be carried out by a known method such as a high pressure method or a melting method, and a multi-site catalyst, a single-site catalyst or the like can be used as a catalyst for the polymerization reaction.
- the bond shape of each monomer is not particularly limited, and a polymer having a bond shape such as a random bond or a block bond can be used.
- the ionomer resin is a resin having an ionic bond between its polymer structures, and an alkali metal or an alkaline earth metal is bonded to a copolymer of ethylene and acrylic acid or methacrylic acid to form a crosslinked structure. Resin can be preferably used.
- the styrene-based resin refers to polystyrene or a copolymer of styrene and one or more other monomers having a styrene content of 50% by mass or more.
- examples of other monomers copolymerized with styrene include acrylonitrile and butadiene.
- Specific examples of the styrene-based resin include polystyrene, a styrene-acrylonitrile copolymer, a styrene-butadiene-acrylonitrile copolymer, and the like.
- the styrene-based resin preferably has a long-chain branch from the viewpoint of cleaning performance, and for example, a resin having a branch can also be used.
- the polycarbonate-based resin is a copolymer having a carbonate ester bond in the repeating unit of the main chain, and is a method for reacting an aromatic dihydroxy compound with a carbonate precursor, an aromatic dihydroxy compound and a carbonate precursor (for example,). , Phosgen) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent (for example, the phosgen method), and an ester exchange method for reacting an aromatic dihydroxy compound with a carbonic acid diester (for example, diphenyl carbonate).
- the polycarbonate-based resin preferably has a long-chain branch from the viewpoint of cleaning performance, and for example, a resin in which branching is introduced by grafting by ionizing irradiation or polymerization can also be used.
- the above-mentioned polyamide-based resin is an aliphatic polyamide-based copolymer or an aromatic polyamide-based copolymer having an amide bond in the repeating unit of the main chain, and is nylon 6, nylon 6/66, or metaxylylene adipamide. (MYD6Ny) and the like can be preferably used.
- the polyester resin is a copolymer having an ester bond in the repeating unit of the main chain, and polyethylene terephthalate or the like obtained by polycondensation of terephthalic acid and ethylene glycol can be preferably used.
- the cleaning agent of the present embodiment may contain an additive.
- the content of the additive is preferably 10% by mass or less with respect to 100% by mass of the detergent composition.
- the additives will be described below.
- the lubricant examples include organic acids, organic acid metal salts, organic acid amides, organic acid derivatives such as organic acid esters, various ester waxes, olefin waxes, fluororesins, mineral oils, etc., but are particularly limited thereto. It's not a thing. From the viewpoint of cleaning performance, the lubricant preferably has a surface tension of 32 mN / m or less, and more preferably a melting point or softening temperature of 70 ° C. or higher.
- the surface tension of zinc stearate is 24 mN / m
- the surface tension of aluminum stearate is 25 mN / m
- the surface tension of polyolefin wax is 32 mN / m, and the like.
- saturated fatty acids having 9 to 28 carbon atoms saturated fatty acids having 9 to 28 carbon atoms, unsaturated fatty acids having 9 to 28 carbon atoms, and benzoic acids are preferable. It may have a hydroxyl group in a part of the chain. In particular, stearic acid, 12-hydroxystearic acid, palmitic acid, myristic acid, and lauric acid are more preferable from the viewpoint of availability and heat resistance. Further, it may be a mixed fatty acid having a different alkyl chain. When the number of carbon atoms is in the above range, there is no problem of gas generation and odor, and it is preferable in that it is easy to obtain and the property as a lubricant at the interface functions well.
- the organic acid may be a metal salt.
- the metal salt in the organic acid metal salt is not particularly limited, and examples thereof include sodium, potassium, lithium, cesium, magnesium, calcium, aluminum, zinc, iron, cobalt, barium salt and the like.
- metal salts of lithium, calcium, barium, zinc or aluminum which are most effective as lubricants, are preferable.
- metal salts of aluminum and zinc have low polarity and easily develop external slipperiness by bleeding out from a thermoplastic resin, which is more preferable.
- Particularly preferred is a zinc metal salt.
- As the hydrocarbon moiety stearic acid or 12-hydroxystearic acid, palmitic acid, myristic acid, and lauric acid are preferable from the viewpoint of availability and heat resistance, as in the case of the chain length of the fatty acid described above.
- organic acid amide examples include saturated fatty acid amides, unsaturated fatty acid amides, saturated fatty acid bisamides, and unsaturated fatty acid bisamides having 9 to 28 carbon atoms.
- fatty acids having 12 to 18 carbon atoms such as lauric acid, myristic acid, palmitic acid, and stearic acid
- amides of unsaturated fatty acids such as erucic acid
- saturated fatty acid bisamides such as ethylene bisstearic acid amide
- organic acid ester and ester wax examples include saturated fatty acid esters having 9 to 28 carbon atoms, unsaturated fatty acid esters, medium-chain fatty acid triglycerides, and polyol esters such as cured oils.
- saturated fatty acid esters having 9 to 28 carbon atoms unsaturated fatty acid esters, medium-chain fatty acid triglycerides, and polyol esters such as cured oils.
- Stearate stearate, glycerin fatty acid ester monoglyceride, and the like are preferable because of their availability and the effect of the lubricant.
- the olefin wax examples include low-molecular-weight polyolefins, and the types are not particularly limited, but general low-density or high-density polyethylene, polypropylene and the like are used.
- the molecular weight has a weight average molecular weight of about 1,000 to 50,000, and a dropping point of 80 to 180 ° C. is most likely to obtain the effect as a lubricant. It is assumed that the thermoplastic resin does not contain the olefin wax of the lubricant.
- the fluorine-based resin examples include PTFE, PFA, PVDF, PVDF-based copolymer, ETFE, PFE, and the like, and the effect of suppressing the resin adhesion to the metal surface can be expected.
- PTFE poly(ethylene glycol)
- PFA poly(ethylene glycol)
- PVDF poly(ethylene glycol)
- PVDF-based copolymer poly(ethylene glycol)
- ETFE terephthalate
- PFE polystylene-based polystyrenephthalate
- the average particle size is not largely limited, but is preferably 1,000 ⁇ m or less. It is assumed that the thermoplastic resin does not contain the fluorine-based resin of the lubricant.
- the above-mentioned mineral oil is an oil obtained by refining petroleum, and is a saturated hydrocarbon-based oil containing naphthene, isoparaffin and the like, which are also called mineral oil, lubricating oil and liquid paraffin.
- Mineral oils with a wide viscosity range can be used.
- the kinematic viscosity measured by JIS K2283 is 50 to 500 mm 2 / s, and the Redwood method (Japan Oil Chemicals Association standard oil and fat analysis test method). Those having a viscosity in the range of 30 to 2000 (seconds) measured according to 2.2.10.4-1996) may be used.
- the above-mentioned lubricants may be used alone or in combination of two or more.
- surfactant examples include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like.
- anion activator examples include higher fatty acid alkali salts, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, and sulfosuccinic acid ester salts.
- cation activator examples include higher amine halides, alkylpyridinium halides, and quaternary ammonium salts.
- non-ionic activator examples include polyethylene glycol alkyl ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid monoglyceride.
- amphoteric surfactant examples include amino acids and the like. The above-mentioned surfactants may be used alone or in combination of two or more.
- the content of additives having a scrubbing effect such as an inorganic filler, an inorganic foaming agent, and an ultra-high molecular weight resin is preferably 9% by mass or less, preferably 7% by mass. It is more preferably% or less, and further preferably 5% by mass or less.
- the effect of the additive having a scrubbing effect on the replaceability is not always clear, but it is considered as follows. That is, the inorganic filler, the inorganic foaming agent, and the ultra-high molecular weight resin improve the detergency by the scraping effect on dirt, while molding when the flow path inside the mold or die such as extrusion molding or injection molding is complicated. Since it easily stays in the machine, it is difficult to discharge it, and it is considered that the replaceability is hindered.
- the inorganic filler means an inorganic compound other than an inorganic foaming agent, and indicates both a natural product and an artificial synthetic product.
- specific examples of such inorganic compounds include talc, mica, wallastonite, zonotrite, kaolin clay, montmorillonite, bentonite, sepiolite, imogolite, cericite, rosonite, smectite, calcium sulfate fiber, calcium carbonate, magnesium carbonate, and oxidation.
- examples thereof include titanium, aluminum hydroxide, magnesium hydroxide, zeolite, calcium clay, glass powder, glass balls, glass fibers, and silas balloons.
- the inorganic foaming agent refers to an inorganic compound that decomposes by heating to generate foam, that is, a gas.
- examples include inorganic physical foaming agents such as water, sodium hydrogen carbonate (hereinafter also referred to as "baking soda"), hydrogen carbonates such as ammonium hydrogen carbonate, carbonates such as sodium carbonate and ammonium carbonate, and nitrites such as ammonium nitrite.
- Hydrogenide such as sodium borohydride, azide compound such as calcium azide, light metal such as magnesium and aluminum, combination of sodium hydrogen carbonate and acid, combination of hydrogen carbonate and yeast, combination of aluminum powder and acid
- Examples thereof include known inorganic chemical foaming agents such as.
- the ultrahigh molecular weight resin is a polymer having a molecular weight of 1 million or more, and examples thereof include ethylene-based superpolymers, styrene-acrylonitrile-based superpolymers, and methyl methacrylate-based superpolymers. Of these, ethylene-based superpolymers are preferable.
- the upper limit of the molecular weight is not particularly limited, but it is generally preferable that the molecular weight is 10 million or less.
- the ultrahigh molecular weight resin may be a homopolymer or a copolymer, and in the case of the copolymer, the content of the main component (for example, ethylene, styrene-acrylonitrile copolymer, methyl methacrylate, etc.) must be 50% by mass or more. ..
- the ultra-high molecular weight resin preferably has a long chain branch from the viewpoint of cleaning performance, and for example, a resin having a branch can also be used. From the viewpoint of detergency and easy replacement, the content of the ultrahigh molecular weight resin is preferably 0.1% by mass or more and 9% by mass or less, preferably 0.2% by mass, based on 100% by mass of the cleaning agent composition.
- Such a cleaning agent composition can achieve both detergency and easy replacement.
- the reason why the above effect is achieved is not always clear, but it is considered as follows. That is, it is considered that the detergency is improved by the effect of scraping off dirt by containing the ultra-high molecular weight resin, but on the other hand, when the content is large, the shear viscosity becomes excessively large and the easy replacement property is hindered. Be done. It is assumed that the thermoplastic resin does not contain the ultra-high molecular weight resin of the additive having the scrubbing effect.
- the cleaning agent for a molding machine of the present embodiment has a branching index of more than 0.30 and less than 1.00 and more than 0.35 and less than 0.97 when the absolute molecular weight determined by light scattering is 1 million. It is preferably more than 0.40 and less than 0.95.
- branching index at an absolute molecular weight of 1,000,000 is in the above range, elongation flow is promoted, and high detergency and easy replacement can be achieved. If the branching index is less than 0.3, there is a risk of gelation and the proportion of side chains is extremely large, so that elongation flow may be suppressed.
- the branching index is 1.00 or more, it means that there is no branching, and the shear flow is the main flow, so that the cleaning effect cannot be expected.
- the branching index at an absolute molecular weight of 1 million can be calculated from the absolute molecular weight and the ultimate viscosity measured by a gel permeation chromatograph (GPC) (for example, PL-GPC220 type high temperature gel permeation chromatograph manufactured by Polymer Laboratories). Specifically, it can be obtained by the method described in Examples described later.
- GPC gel permeation chromatograph
- the cleaning performance of the cleaning agent is determined by the elongation viscosity and shear viscosity measured by a twin capillary rheometer (narrowing viscometer) (for example, Malvern RH10), and the rheometer (for example, TA Instruments). Since it depends on the storage elastic modulus measured by ARES-G2), it is necessary to adjust both the viscosity and elasticity at the temperature range during molding, the shear rate, and the angular velocity. Further, in the present embodiment, in order to achieve high detergency and easy replacement, viscoelasticity at the time of melting is important, and particularly in cleaning of a molding machine, if the extensional viscosity of the entire cleaning agent composition is high. The extensional flow is promoted, and the molding material used in the previous molding can be easily switched to the cleaning agent.
- viscosity is evaluated by shear viscosity and elasticity is evaluated by extensional viscosity.
- the shear rate range of the cleaning agent of the present embodiment is several tens to several hundreds of sec -1 , and the shear rate having a high correlation with the cleaning performance of extrusion processing is 100 sec -1 .
- the extensional viscosity of the entire cleaning agent composition is high in order to achieve high detergency with respect to the molding material used in the previous molding.
- the extensional viscosity of the detergent composition is preferably 42 to 150 kPa ⁇ s, more preferably 50 to 140 kPa ⁇ s, and 55 to 55 to 140 kPa ⁇ s. It is more preferably 130 kPa ⁇ s.
- thermoplastic resin having a long-chain branched structure is preferably contained in an amount of 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and 15% by mass or less. It is more preferable to contain more than 50% by mass or less.
- Such a cleaning agent composition can have the above-mentioned extensional viscosity and can easily switch from the molding material used in the previous molding to the cleaning agent.
- the reason why the above effect is exerted is not always clear, but it is considered that the material substitution can be promoted by expressing a circulating flow like a vortex by the extensional flow due to the extensional viscosity.
- the content of the resin having a long-chain branched structure is less than 5% by mass, it is difficult to sufficiently improve the extensional viscosity, and when it is 75% by mass or more, the storage elastic modulus of the entire detergent composition tends to decrease. In all cases, sufficient cleaning performance tends not to be obtained.
- FIG. 1 shows a conceptual diagram of the twin capillary rheometer.
- the twin capillary rheometer has two barrels 2 and two pistons 1, and has different L (length) / d (diameter) dies (long die 4 and short die 5) on the left and right sides.
- the pressure change accompanying the change in the shear rate is measured with the pressure gauge 3 on the barrel side closest to the die, and the extensional viscosity is determined by the following Cogswell theoretical formula (Polymer Engineering Science, 12, 64 (1972)).
- the storage elastic modulus of the cleaning agent composition is preferably 80 to 250 kPa, more preferably 90 to 240 kPa at a temperature of 190 ° C. and an angular velocity of 100 rad / sec, 100. It is more preferably about 230 kPa.
- Such a cleaning agent composition can have high cleaning performance. The reason why the above effect is obtained is not always clear, but the cleaning agent composition having a high storage elastic modulus easily discharges the molding material used in the previous molding, which is affected by the hardness of the cleaning agent at the time of melting. It was found that the storage elastic modulus at an angular velocity of 100 rad / sec has a good correlation with the cleaning performance.
- the storage elastic modulus of the detergent composition can be measured by the method described in Examples described later.
- the cleaning agent is also required to be easily replaceable with respect to replacement of the cleaning agent with a molding material used for the next molding. Therefore, in order to improve the ease of substitution, the shear viscosity of the detergent composition is preferably 500 to 1400 Pa ⁇ s at a temperature of 190 ° C. and a shear rate of 100 sec -1, preferably 550 to 1350 Pa ⁇ s. More preferably, it is 600 to 1300 Pa ⁇ s.
- the detergent composition having such a shear viscosity has high replaceability and can be easily switched from the detergent to the next molding material.
- thermoplastic resin having a low molecular weight or a wide molecular weight distribution, and these may be achieved by combining two or more kinds of thermoplastic resins. Since such a detergent composition has high fluidity, it is considered that it is easy to switch to the next molding material.
- the shear viscosity at a shear rate of 100 sec -1 and a temperature of 190 ° C. can be measured by the method described in Examples described later.
- extensional viscosity is relative to the shear viscosity at a temperature of 190 ° C. and a shear rate of 100 sec -1.
- the ratio (extensional viscosity (Pa ⁇ s) / shear viscosity (Pa ⁇ s)) is preferably 30 or more, the extensional viscosity / shear viscosity is more preferably 35 or more, and the extensional viscosity / shear viscosity is 40 or more. Is more preferable.
- Such a cleaning agent composition has high cleaning performance, and the cleaning agent can be easily switched to the molding material to be molded next.
- thermoplastic resin it is preferable to reduce the molecular weight of the thermoplastic resin and increase the entanglement of the molecular chains such as introducing a long chain branched structure into the thermoplastic resin.
- the cleaning agent composition of the present embodiment is suitable for cleaning applications of injection molding and extrusion molding having a complicated flow path, and above all, it is more suitable for cleaning after processing of a molded product containing polyolefin.
- the method for producing the detergent composition of the present embodiment is not particularly limited, and for example, it can be produced by a method such as premixing each of the above components with a mixer, kneading and extruding with an extruder, and pelletizing.
- the shape of the cleaning agent of the present embodiment is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a columnar shape, a spherical shape, a flake shape, and a powder shape.
- the cleaning method of the resin molding processing machine As the cleaning method of the resin molding processing machine according to the present embodiment, the above-mentioned detergent composition is used. Further, the cleaning method of the resin molding processing machine according to the present embodiment may include a step of retaining the above-mentioned cleaning agent composition in the resin molding processing machine. Specific examples of the resin molding machine include an injection molding machine, an extrusion molding machine, and the like.
- the cleaning method of the resin molding processing machine according to the present embodiment can not only efficiently discharge the material formed before cleaning, but also when the resin molding processing machine is stopped after cleaning, the cleaning agent composition is made of resin. By staying filled in the molding machine, even if the material molded before cleaning remains in the resin molding machine due to insufficient cleaning, there is an advantage that the remaining material can be prevented from thermal deterioration. be.
- the mobile phase solvent was 1,2,4-trichlorobenzene (with antioxidant BHT added), the flow rate was 1 mL / min, and the column was TSKgel GMHR- manufactured by Toso. Two H (S) and one TSKgel GHHR-M (S) were used.
- the temperature of the column, the sample injection part and each detector was 140 ° C., the sample concentration was 1 mg / mL, and the injection amount was 0.5 mL.
- a sintered filter having a pore size of 1 ⁇ m was used for sample filtration.
- the absolute molecular weight and the ultimate viscosity of each cleaning agent composition were calculated using polystyrene having a molecular weight of 190,000 manufactured by Tosoh for equipment calibration.
- the branching index is the ultimate viscosity ([ ⁇ ] br) obtained by measuring the linear polymer of the limit viscosity ([ ⁇ ] br) obtained by measuring with the above viscometer when the absolute molecular weight obtained by light scattering is 1 million. It was calculated as a ratio ([ ⁇ ] br / [ ⁇ ] lin) to [ ⁇ ] lin).
- the linear polymer is Nist's linear low-density polyethylene 1475a for polyethylene resin, American Polymer Standards PP210K for polypropylene resin, and Tosoh monodisperse polystyrene (molecular weight 190,000) for polystyrene resin. ) was used.
- a mixture in which the corresponding linear polymers were mixed at the same component ratio was used. Since it is known as Mark-Houwink-lot that the logarithm of [ ⁇ ] lin of a linear polymer has a linear relationship with the logarithm of molecular weight, [ ⁇ ] lin is on the low molecular weight side or the high molecular weight side. Numerical values can be obtained by extrapolating as appropriate.
- the branching index becomes smaller as the molecular weight becomes larger, it is judged that the long chain branching exists.
- composition analyzer manufactured by Polymer Char
- IR5 MCT infrared detector manufactured by Polymer
- the moving solvent is 1,2-dichlorobenzene (addition of antioxidant BHT)
- the column is a CEF column (manufactured by Polymer Char, length 150 mm, capacity 2.3 mL
- detection wavelength is methylene sensor CH 2 3.42 ⁇ m (2920 cm -1).
- Methyl sensor CH 3 3.38 ⁇ m (2960 cm -1 ) was used.
- the sample concentration was 16 mg / 8 mL
- the dissolution conditions were 150 ° C., 60 min, N 2 atmosphere
- the sample was filtered using a 1.0 ⁇ m in-line filter.
- the injection volume is 0.2 mL
- the temperature lowering condition is 95 ° C ⁇ -20 ° C, 1.0 ° C / min
- the flow rate is 0.012 mL / min
- the temperature raising condition is -20 ° C ⁇ 160 ° C, 4.0 ° C / min.
- the component ratio (mass%) of the thermoplastic resin having a long-chain branched structure in the cleaning agent composition was determined from the peak area of the elution curve at a flow rate of 1.0 mL / min.
- a blue-colored low-density polyethylene (Suntech M1920 manufactured by Asahi Kasei Co., Ltd.) was used as a colored masterbatch, and 10 parts by mass of the colored masterbatch and 90 parts by mass of high-density polyethylene (Suntech B871 manufactured by Asahi Kasei Co., Ltd.) were mixed. 3 kg was put into a blow molding machine (JEB-7 manufactured by Nippon Steel Works), the screw was rotated to discharge the resin mixture from the die, and pseudo stains were attached to the inside of the molding machine.
- JEB-7 blow molding machine
- the raw materials used in the examples and comparative examples are as follows.
- HD1 High-density polyethylene (Suntech B770 manufactured by Asahi Kasei Co., Ltd.), no long-chain branch HD2: High-density polyethylene (Novatec HB420R manufactured by Nippon Polyethylene Co., Ltd.), with long-chain branch HD3: High-density polyethylene (manufactured by Toso Co., Ltd.) Nipolon Hard 6900B), no long-chain branch HD4: high-density polyethylene (Hi-Zex 5000SR manufactured by Mitsui Kagaku Co., Ltd.), no long-chain branch HD5: high-density polyethylene (Hi-Zex 6200B manufactured by Mitsui Kagaku Co., Ltd.), no long-chain branch LD1: Low density polyethylene (Suntech M2102 manufactured by Asahi Kasei Co., Ltd.), with long chain branch LD2: Low density polyethylene (Petrosen 219 manufactured by Toso Co., Ltd.),
- Inorganic foaming agent 1 Sodium bicarbonate Cal: Calcium carbonate (TW-300s manufactured by Okutama Kogyo Co., Ltd.) GF: Glass fiber (ECS-03-T-120 manufactured by Nippon Electric Glass Co., Ltd.) Talc: Talc (PHSH talc manufactured by Takehara Chemical Industry Co., Ltd.) AL (OH) 3 : (Heidi Light H-32 manufactured by Showa Light Metal Co., Ltd.) PEO: Polyethylene oxide (Alcox R-1000 manufactured by Meisei Kagaku Co., Ltd.) AB1: Lubricants (Alflow H-50F manufactured by NOF CORPORATION) AB2: Lubricants (Magnesium stearate SM-PG manufactured by Sakai Chemical Co., Ltd.) AB3: Lubricating agent (calcium borate ester calcium salt of monoglyceride stearate) AB4: Lubricants (basic magnesium carbonate manufactured by Sakai Chemical Co.,
- Example 1 A composition containing LD1 as a thermoplastic resin, AB1 as a lubricant, and SU1 as a surfactant in the proportions shown in Table 1 was premixed in advance using a tumbler blender for 5 minutes, and the obtained mixture was mixed by a twin-screw extruder. Smelted. A twin-screw extruder (TEM26SS manufactured by Toshiba Machine Co., Ltd.) was used for kneading, and the kneading was carried out under the conditions of an extrusion temperature of 240 ° C. and an extrusion rate of 20 kg / hour. The melt-kneaded product thus obtained was extruded into a strand shape, cooled with water, and then cut with a strand cutter to obtain a pellet-shaped detergent composition. The evaluation results of the obtained detergent composition are shown in Table 1.
- Examples 2 to 12 A pellet-shaped detergent composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 1. The evaluation results of the obtained detergent composition are shown in Table 1.
- Example 1 A pellet-shaped detergent composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 2. The evaluation results of the obtained detergent composition are shown in Table 2.
- the cleaning agent composition for a resin molding machine of the present invention exhibits excellent cleaning performance and also has excellent replaceability, and is used for cleaning thermoplastic resins, particularly, a cleaning agent composition for injection molding and extrusion molding machines. It is useful as a thing.
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Abstract
Description
上記(1)の方法は、成形加工機械を停止する必要があるため効率的でなく、且つ人手により物理的に除去作業をするため、成形加工機械を傷つけやすいという問題がある。上記(2)の方法は、残留物を除去するために多量の成形材料を必要とする場合が多く、作業が完了するまでに時間を要し、更に廃棄物が多量に発生するという問題がある。そこで近年では、上記(3)の洗浄剤を用いる方法が、成形加工機械内の残留物を除去する洗浄力に優れることから、好まれて用いられるようになっている。
[1]
長鎖分岐構造を有する熱可塑性樹脂を含み、絶対分子量100万における分岐指数が0.30超1.00未満であることを特徴とする、成形機用洗浄剤。
[2]
せん断速度100sec-1における190℃の伸長粘度の、せん断速度100sec-1における190℃のせん断粘度に対する割合(伸長粘度/せん断粘度)が30以上である、[1]に記載の成形機用洗浄剤。
[3]
せん断速度100sec-1における190℃の伸長粘度が42~150kPa・sであり、且つせん断速度100sec-1における190℃のせん断粘度が500~1400Pa・sである、[1]又は[2]に記載の成形機用洗浄剤。
[4]
前記長鎖分岐構造を有する熱可塑性樹脂を5質量%以上70質量%以下含む、[1]~[3]のいずれかに記載の 成形機用洗浄剤。
[5]
角速度100rad/secにおける190℃の貯蔵弾性率が80kPa以上である、[1]~[4]のいずれかに記載の成形機用洗浄剤。
[6]
スクラブ効果を有する添加剤の含有量が9質量%以下である、[1]~[5]のいずれかに記載の成形機用洗浄剤。
[7]
融点が130℃以上の熱可塑性樹脂を含む、[1]~[6]のいずれかに記載の成形機用洗浄剤。
本実施形態の成形機用洗浄剤(本明細書において、単に「洗浄剤」又は「洗浄剤組成物」と称する場合がある。)は、長鎖分岐構造を有する熱可塑性樹脂を含み、絶対分子量100万における分岐指数が0.30超1.00未満である。該洗浄剤は、滑剤、界面活性剤等の添加剤を更に含んでよい。
本実施形態の成形機用洗浄剤に含まれる熱可塑性樹脂は、長鎖分岐構造を有する熱可塑性樹脂を含む。長鎖分岐構造を有する熱可塑性樹脂のみからなるものであっても、長鎖分岐構造を有する熱可塑性樹脂と長鎖分岐構造を有しない熱可塑性樹脂との混合物であってもよい。
なお、長鎖分岐構造とは主鎖と比肩しうる長さの分岐であり、一方で短鎖分岐とは炭素数が数個までの長さの分岐を意味するものとする。
上記効果が奏される理由は必ずしも明らかではないが、以下のように考えられる。すなわち、従来の洗浄剤の流動は、せん断流動に支配され、ダイ内部のデッドスペース等で成形材料や洗浄剤が滞留しやすいが、本実施形態の洗浄剤では、分子鎖の絡まりに起因する伸長流動によって渦のような循環流を発現させることで材料置換を促すことができると考えられる。そのため、伸長流動を促すことを目的に、本実施形態の成形機用洗浄剤は、予め長鎖分岐構造を有する熱可塑性樹脂を含むものとする、或いは、長鎖分岐構造を有しない熱可塑性樹脂に長鎖分岐構造を導入することにより、長鎖分岐構造を有する熱可塑性樹脂を含むものとする。また、さらに、熱可塑性樹脂の分子量を増加させた熱可塑性樹脂、架橋点又は疑似架橋点を有する熱可塑性樹脂を含むことが好ましく、これら2種以上の熱可塑性樹脂を組み合わせてもよい。このような洗浄剤組成物は、分子鎖の絡まりが増加することで伸長流動が促されると考えられる。
熱可塑性樹脂に長鎖分岐構造を導入する方法としては、特に限定されず、個々の熱可塑性樹脂において従来公知の方法を用いることができる。
また、上記エチレン-α-オレフィン共重合体としては、エチレンと、プロピレンコモノマー、ブテンコモノマー、ヘキセンコモノマー及びオクテンコモノマーから選ばれる少なくとも1種のコモノマーとの共重合体が、一般に入手が容易であり、好適に使用できる。
上記ポリエチレン系樹脂は、1種を単独で、又は2種以上を組み合わせて用いることができる。洗浄性能の観点から、長鎖分岐構造を有するポリエチレン系樹脂であることがより好ましい。
また、上記ポリプロピレン系樹脂は、洗浄性能の観点から長鎖分岐を有することが好ましく、例えば、電離性放射線照射によるグラフト化や重合によって分岐を導入することができる。
上記ポリブテン系樹脂としては、結晶性であり、ブテンと、エチレン、プロピレン及び炭素数5~8のオレフィン系化合物から選ばれる少なくとも1種からなる共重合体が好適に使用できる。
更に、エチレン-脂肪族不飽和カルボン酸エステル共重合樹脂とは、エチレンモノマーと、脂肪族不飽和カルボン酸エステルから選ばれる少なくとも1種のモノマーとの共重合により得られる共重合体を示す。脂肪族不飽和カルボン酸エステルとしては、例えば、アクリル酸エステル、メタクリル酸エステル、フマル酸エステル、マレイン酸エステル等が挙げられる。
上記共重合樹脂の共重合は、高圧法、溶融法等の公知の方法により行うことができ、重合反応の触媒としてマルチサイト触媒やシングルサイト触媒等を用いることができる。また、上記共重合体において、各モノマーの結合形状は特に限定されず、ランダム結合、ブロック結合等の結合形状を有するポリマーを使用することができる。
スチレンと共重合させる他の単量体としては、例えば、アクリロニトリル、ブタジエン等が挙げられる。
スチレン系樹脂の具体例としては、ポリスチレン、スチレン-アクリロニトリル共重合体、スチレン-ブタジエン-アクリロニトリル共重合体等が挙げられる。
上記スチレン系樹脂は、洗浄性能の観点から長鎖分岐を有することが好ましく、例えば、分岐を有する樹脂等も使用できる。
上記ポリカーボネート系樹脂は、洗浄性能の観点から長鎖分岐を有することが好ましく、例えば、電離性放射線照射によるグラフト化や重合によって分岐が導入された樹脂等も使用できる。
添加剤の含有量は、洗浄剤組成物100質量%に対して10質量%以下であることが好ましい。
以下に添加剤について説明する。
滑剤としては、有機酸、有機酸金属塩、有機酸アミド、有機酸エステル等の有機酸誘導体、各種エステルワックス、オレフィンワックス、フッ素系樹脂、ミネラルオイル等が挙げられるが、これらに特に限定されるものではない。
滑剤は、洗浄性能の観点から、表面張力が32mN/m以下であることが好ましく、融点又は軟化温度が70℃以上であることがより好ましい。例えば、ステアリン酸亜鉛の表面張力は24mN/m、ステアリン酸アルミニウムの表面張力は25mN/m、ポリオレフィンワックスの表面張力は32mN/m等となっている。
炭化水素部位は、先に記述の脂肪酸の鎖長と同じく、入手のしやすさ、耐熱性の観点から、ステアリン酸あるいは12-ヒドロキシステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸が好ましい。
なお、上記熱可塑性樹脂に、上記滑剤のオレフィンワックスは含まれないものとする。
なお、上記熱可塑性樹脂に、上記滑剤のフッ素系樹脂は含まれないものとする。
上述の滑剤は、1種単独で用いてもよく、2種以上併用してもよい。
上記界面活性剤の例としては、陰イオン活性剤、陽イオン活性剤、非イオン活性剤、両性表面活性剤等が挙げられる。陰イオン活性剤としては、具体的には、高級脂肪酸アルカリ塩、アルキル硫酸塩、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、スルホコハク酸エステル塩等が例示できる。陽イオン活性剤としては、具体的には、高級アミンハロゲン酸塩、ハロゲン化アルキルピリジニウム、第四アンモニウム塩等が例示できる。非イオン活性剤としては、具体的には、ポリエチレングリコールアルキルエ-テル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド
等が例示できる。両性表面活性剤としては、具体的には、アミノ酸等を例示する事ができる。
上述の界面活性剤は、1種単独で用いてもよく、2種以上併用してもよい。
スクラブ効果を有する添加剤の置換性に対する効果は必ずしも明らかではないが、以下のように考えられる。すなわち、無機フィラーや無機発泡剤、超高分子量樹脂は、汚れに対する掻き取り効果によって洗浄力を向上させる一方で、押出成形や射出成形等の金型やダイ内部の流路が複雑な場合は成形機内に滞留しやすいため排出が困難であり、置換性が阻害されると考えられる。
(無機フィラー)
本実施形態において、無機フィラーとは、無機発泡剤以外の無機化合物をいい、天然物及び人工合成物のいずれも示す。このような無機化合物の具体例としては、タルク、マイカ、ワラストナイト、ゾノトライト、カオリンクレー、モンモリロナイト、ベントナイト、セピオライト、イモゴライト、セリサイト、ローソナイト、スメクタイト、硫酸カルシウム繊維、炭酸カルシウム、炭酸マグネシウム、酸化チタン、水酸化アルミニウム、水酸
化マグネシウム、ゼオライト、ケイソウ土、ガラス粉末、ガラス球、ガラス繊維、シラスバルーン等が挙げられる。
本実施形態において、無機発泡剤とは、加熱により分解し、発泡、すなわち気体を発生する無機化合物を指す。例としては、水等の無機物理発泡剤、炭酸水素ナトリウム(以下「重曹」とも記す。)、炭酸水素アンモニウム等の炭酸水素塩、炭酸ナトリウム、炭酸アンモニウム等の炭酸塩、亜硝酸アンモニウム等の亜硝酸塩、ホウ水素化ナトリウム等の水素化物、アジ化カルシウム等のアジド化合物、マグネシウム、アルミニウム等の軽金属、炭酸水素ナトリウムと酸との組合せ、過酸化水素とイースト菌との組合せ、アルミニウム粉末と酸との組合せ等の公知の無機化学発泡剤が挙げられる。
本実施形態において、超高分子量樹脂とは、分子量100万以上の高分子であり、例えば、エチレン系超高分子、スチレン-アクリロニトリル系超高分子、メタクリル酸メチル系超高分子等が挙げられるが、中でもエチレン系超高分子が好ましい。分子量の上限は特に限定されないが、一般的には1000万以下であることが実用上好ましい。
また、超高分子量樹脂はホモポリマーでもコポリマーでもよく、コポリマーの場合は主成分(例えば、エチレン、スチレン-アクリロニトリル共重合体、メタクリル酸メチル等)の含有量が50質量%以上である必要がある。
上記超高分子量樹脂は、洗浄性能の観点から長鎖分岐を有することが好ましく、例えば、分岐を有する樹脂等も使用できる。
洗浄力と易置換性の観点から、超高分子量樹脂の含有量は、洗浄剤組成物100質量%に対して、0.1質量%以上9質量%以下であることが好ましく、0.2質量%以上7質量%以下であることがより好ましく、0.3質量%以上5質量%以下であることが更に好ましい。このような洗浄剤組成物は、洗浄力と易置換性を両立することができる。
上記効果が奏される理由は必ずしも明らかではないが、以下のように考えられる。すなわち、超高分子量樹脂を含有することで汚れの掻き取り効果によって洗浄力が向上するが、一方で含有量が多くなると、せん断粘度が過度に大きくなるため、易置換性が阻害されると考えられる。
なお、上記熱可塑性樹脂に、上記スクラブ効果を有する添加剤の超高分子量樹脂は含まれないものとする。
上記分岐指数を0.30超1.00未満にする方法としては、長鎖分岐を多く導入するなど、分子鎖の絡まりを増加させることが挙げられる。
なお、絶対分子量100万における分岐指数は、ゲル浸透クロマトグラフ(GPC)(例えば、Polymer Laboratories社製PL-GPC220型高温ゲル浸透クロマトグラフ)で測定される絶対分子量及び極限粘度から算出することができ、具体的には、後述の実施例に記載の方法により求めることができる。
また、本実施形態において、高洗浄力及び易置換性を達成するためには、溶融時の粘弾性が重要であり、特に、成形機の洗浄において、洗浄剤組成物全体の伸長粘度が高ければ伸長流動が促され、前の成形で使用した成形材料から洗浄剤へ容易に切り替えることができる。
洗浄剤組成物の伸長粘度を上記範囲とするためには、熱可塑性樹脂への長鎖分岐構造の導入や熱可塑性樹脂の分子量、分岐度、分子量分布、及び超高分子量樹脂の添加の有無等の選択、調整が挙げられ、特に、長鎖分岐構造を有する熱可塑性樹脂を5質量%以上70質量%以下含むことが好ましく、10質量%以上60質量%以下含むことがより好ましく、15質量%以上50質量%以下含むことが更に好ましい。このような洗浄剤組成物であれば、上述の伸長粘度を有することができ、前の成形で使用した成形材料から洗浄剤へ容易に切り替えることができる。
上記効果が奏される理由は必ずしも明らかではないが、伸長粘度に起因する伸長流動によって渦のような循環流を発現させることで材料置換を促すことができると考えられる。長鎖分岐構造を有する樹脂の含有量が5質量%未満の場合は十分な伸長粘度向上が困難であり、75質量%以上の場合は洗浄剤組成物全体の貯蔵弾性率が低下する傾向となり、いずれも十分な洗浄性能が得られなかい傾向にある。
伸長粘度λ[kPa・s]=9(n+1)2Po2/(32ηγ2)
せん断粘度η[kPa・s]=Tc/γ
みかけのせん断速度γ[s-1]=4Q/((πd3)/8)
補正したせん断応力Tc[kPa]=(Pl-Po)d/4L
(式中、Q:容積流量、d:ダイの細管直径(mm)、Pl:ロングダイス側圧力損失、Ps:ショートダイス測定圧力損失、Po:ショートダイス側厚みゼロ換算圧力、或いはPl-Psの値から外挿して得られるL/d=0の圧力、n:パワーロー指数(n=1、2、3、4・・・)を表す。)
なお、データの補正は、Bagley補正のみを使用し、Rabinowitsch補正は使用しないものとする。
洗浄剤組成物の上記伸長粘度は、具体的には、後述の実施例に記載の方法により測定することができる。
上記効果が奏される理由は必ずしも明らかではないが、貯蔵弾性率が高い洗浄剤組成物は前の成形で使用した成形材料を排出し易く、これは溶融時の洗浄剤の固さが影響していると考えられ、特に角速度100rad/secの貯蔵弾性率が洗浄性能と良い相関関係になることを見出した。
上記効果が奏される理由は必ずしも明らかではないが、洗浄剤組成物の貯蔵弾性率の向上が洗浄性能に影響していると考えられる。
なお、洗浄剤組成物の上記貯蔵弾性率は、具体的には、後述の実施例に記載の方法により測定することができる。
なお、せん断速度100sec-1、温度190℃におけるせん断粘度は、後述の実施例に記載の方法により測定することができる。
上記効果が奏される理由は必ずしも明らかではないが、上述の伸長流動による前の成形材料の排出と、せん断粘度が低いことによる洗浄剤自体の排出を両立することができるためと考えられる。上記を達成するためには、熱可塑性樹脂の分子量を低下させる一方で、熱可塑性樹脂に長鎖分岐構造を導入する等の分子鎖の絡まりを増加させることが好ましい。
本実施態様の洗浄剤組成物の製造方法は、特に限定されないが、例えば、上記各成分を混合機で予備混合した後、押出機で混練押出し、ペレタイズする方法等により製造することができる。
本実施形態の洗浄剤の形状は、本発明の効果を阻害しない限り特に限定されないが、例えば、円柱状、球状、フレーク状、パウダー状等の形状が挙げられる。
本実施形態に係る樹脂成形加工機械の洗浄方法は、上述の洗浄剤組成物を用いる。
また、本実施形態に係る樹脂成形加工機械の洗浄方法は、上述の洗浄剤組成物を樹脂成形加工機械内に滞留させる工程を有してもよい。
上記樹脂成形加工機械の具体例としては、射出成形機、押出成形機等が挙げられる。
本実施形態に係る樹脂成形加工機械の洗浄方法は、洗浄前に成形加工した材料を効率的に排出させることができるだけでなく、洗浄後に樹脂成形加工機械を休止する場合、洗浄剤組成物を樹脂成形加工機械内に充満させた状態で滞留させることにより、万が一洗浄不足で洗浄前に成形加工した材料が樹脂成形加工機械内に残っている場合でも、残った材料の熱劣化を防止できる利点がある。
[分岐指数]
ゲル浸透クロマトグラフとして、装置内蔵の示差屈折計、PD2040型2角度光散乱光度計(Precision Detectors社製)、及びPL-BV400型ブリッジ型粘度計(Polymer Laboratories社製)を装備したPL-GPC220型高温ゲル浸透クロマトグラフ(Polymer Laboratories社製)を用い、移動相溶媒は、1,2,4-トリクロロベンゼン(酸化防止剤BHT添加)、流量は1mL/分、カラムは、東ソー社製TSKgel GMHHR-H(S)を2本とTSKgel GHHR-M(S)1本とした。カラム、試料注入部および各検出器の温度は、140℃、試料濃度は1mg/mLとし、注入量は0.5mLとした。試料ろ過には孔径1μmの焼結フィルターを用いた。装置校正に東ソー製の分子量190,000のポリスチレンを用いて、各洗浄剤組成物の絶対分子量、極限粘度を算出した。
分岐指数は、光散乱によって求めた絶対分子量が100万の時の上記粘度計で測定して得られた極限粘度([η]br)の、線状ポリマーを測定して得られた極限粘度([η]lin)に対する比率([η]br/[η]lin)として算出した。
線状ポリマーは、ポリエチレン系樹脂については、Nist製の直鎖状低密度ポリエチレン1475aを、ポリプロピレン系樹脂についてはAmerican Polymer Standards製PP210Kを、ポリスチレン系樹脂については東ソー製単分散ポリスチレン(分子量190,000)を用いた。なお、複数種類の熱可塑性樹脂を用いた場合は、それぞれに対応する線状ポリマーを同じ成分比率で混合した混合物を用いた。
なお、線状ポリマーの[η]linの対数は分子量の対数と線形の関係があることは、Mark-Houwink-plotとして公知であるから、[η]linは、低分子量側や高分子量側に適宜外挿して数値を得ることができる。
また、分子量が大きくなるほど分岐指数が小さくなる場合に、長鎖分岐が存在すると判断した。
ツインキャピラリーレオメータ(Malvern社製RH10)を用い、温度190℃にて、ロングダイス(L/d=16、直径1mm、流入角90°)及びショートダイス(L/d=0.25、直径1mm、流入角90°)のオリフィスダイを使用して、ツインバーグレーの測定モードにて、せん断速度100s-1についてせん断応力を測定し、下記Cogswellの理論式(Polymer Engineering Science、12、64(1972))に従って伸長粘度λ(kPa・s)及びせん断粘度η(Pa・s)を求めた。
なお、データの補正は、Bagley補正のみを使用し、Rabinowitsch補正は使用しなかった。
伸長粘度λ[kPa・s]=9(n+1)2Po2/(32ηγ2)
せん断粘度η[kPa・s]=Tc/γ
みかけのせん断速度γ[s-1]=4Q/((πd3)/8)
補正したせん断応力Tc[kPa]=(Pl-Po)d/4L
(式中、Q:容積流量、d:ダイの細管直径(mm)、Pl:ロングダイス側圧力損失、Ps:ショートダイス側圧力損失、Po:ショートダイス側厚みゼロ換算圧力、或いはPl-Psの値から外挿して得られるL/d=0の圧力、n:パワーロー指数(n=1、2、3、4・・・)を表す。)
レオメータ(TAインスツルメント社製ARES-G2)を用い、温度190℃にて、パラレルプレート(直径25mm)、窒素雰囲気下、ギャップ1.0~2.0mm、ひずみ0.3~1.0%で、角速度100rad/secについて、貯蔵弾性率(kPa)を測定した。
組成分析には、結晶化溶出分別によるクロマトグラフとして、装置内蔵のIR5 MCT赤外検出器(Polymer Char社製)を装備したハイスループット組成分析装置(Polymer Char社製)を用いた。移動溶媒は1,2-ジクロロベンゼン(酸化防止剤BHT添加)、カラムはCEFカラム(Polymer Char社製、長さ150mm、容量2.3mL、検出波長はメチレンセンサ CH2 3.42μm(2920cm-1)、メチルセンサー CH3 3.38μm(2960cm-1)を用いた。試料濃度は16mg/8mL、溶解条件は150℃、60min,N2雰囲気化とし、試料ろ過は1.0μmインラインフィルターを用いた。注入量は0.2mLとし、降温条件は95℃→-20℃、1.0℃/min、流量0.012mL/min、昇温条件は-20℃→160℃、4.0℃/min、流量1.0mL/minにて、溶出曲線のピーク面積から洗浄剤組成物中の長鎖分岐構造を有する熱可塑性樹脂の成分比率(質量%)を求めた。
青色に着色された低密度ポリエチレン(旭化成(株)製サンテックM1920)を着色マスターバッチとし、着色マスターバッチ10質量部と高密度ポリエチレン(旭化成(株)製サンテックB871)90質量部とを混合し、ブロー成形機(日本鉄鋼所製JEB-7)に3kg投入して、スクリューを回転させて当該樹脂混合物をダイから排出して成形機内に疑似的な汚れを付着させた。
その後、当該成形機に実施例及び比較例で得られた洗浄剤組成物を4kg投入し、シリンダー温度190℃及びダイ温度190℃の条件でスクリュー回転により洗浄した。ダイから排出されるパージ屑の色調を目視にて観察しながら、洗浄が完了するまでパージ屑を排出し、排出されたパージ屑量(kg)を天秤で測定した。当該排出されたパージ屑量が少ないほど、洗浄性に優れるとし、以下の評価基準で評価した。
なお、洗浄した際にダイから排出されるパージ屑を室温まで冷却して固化させたものの色調が、青色から洗浄剤組成物の色に変わった時点を洗浄完了とした。
[評価基準]
A:パージ屑量が2.6kg以下であり、洗浄性が特に良好
B:パージ屑量が2.6kg超2.8kg以下であり、洗浄性がより良好
C:パージ屑量が2.8kg超3.0kg以下であり、洗浄性が良好
D:パージ屑量が3.0kgより多く、洗浄が困難
上記の<洗浄性評価>の後、高密度ポリエチレン(旭化成(株)製サンテックB871)を上記ブロー成形機に4kg投入し、シリンダー温度190℃及びダイ温度190℃の条件でスクリュー回転により置換し、ダイから排出される溶融樹脂の外観の色調を目視にて観察しながら、置換が完了するまでパージ屑を排出し、排出されたパージ屑量(kg)を天秤で測定した。当該排出されたパージ屑量が少ないほど、置換性に優れるとし、以下の評価基準で評価した。
なお、置換の際にダイから排出される溶融状態のパージ屑の外観の色調が、洗浄剤組成物の色から透明に変わった時点を置換完了とした。
[評価基準]
A:パージ屑量が1.5kg未満であり、置換性が良好
D:パージ屑量が1.5kg以上であり、洗浄剤の置換が困難
HD1:高密度ポリエチレン(旭化成(株)製サンテックB770)、長鎖分岐なし
HD2:高密度ポリエチレン(日本ポリエチレン(株)製ノバテックHB420R)、長鎖分岐あり
HD3:高密度ポリエチレン(東ソー(株)製ニポロンハード6900B)、長鎖分岐なし
HD4:高密度ポリエチレン(三井化学(株)製ハイゼックス5000SR)、長鎖分岐なし
HD5:高密度ポリエチレン(三井化学(株)製ハイゼックス6200B)、長鎖分岐なし
LD1:低密度ポリエチレン(旭化成(株)製サンテックM2102)、長鎖分岐あり
LD2:低密度ポリエチレン(東ソー(株)製ペトロセン219)、長鎖分岐あり
LL1:線状低密度ポリエチレン(日本ポリエチレン(株)製ノバテックUF320)、長鎖分岐なし
LL2:線状低密度ポリエチレン(三井化学(株)製エボリューSP3010、長鎖分岐なし
LL3:線状低密度ポリエチレン((株)NUC製GS650)、長鎖分岐なし
EEA:エチレン・アクリル酸エチル共重合体(三井デュポンケミカル(株)製エバフレックスAN4214C)、長鎖分岐なし
PP1:ポリプロピレンホモポリマー(サンアロマー(株)製VS200A)、長鎖分岐なし
MAH-PS:スチレン-マレイン酸共重合体(第一工業製薬(株)製ニューフロンティアMI-400P)、長鎖分岐なし
MMSC:メタクリル酸メチル-スチレン共重合体(第一工業製薬(株)ニューフロンティアMS-750P、長鎖分岐なし
無機発泡剤1:炭酸水素ナトリウム
炭カル:炭酸カルシウム(奥多摩工業(株)製TW-300s)
GF:ガラス繊維(日本電気硝子(株)製ECS-03-T-120)
タルク:タルク(竹原化学工業(株)製PHSHタルク)
AL(OH)3:(昭和軽金属(株)製ハイジライトH-32)
PEO:ポリエチレンオキサイド(明成化学(株)製アルコックスR-1000)
AB1:滑剤(日油(株)製アルフローH-50F)
AB2:滑剤(堺化学(株)製ステアリン酸マグネシウムSM-PG)
AB3:滑剤(ステアリン酸モノグリセライドのホウ酸エステルカルシウム塩)
AB4:滑剤(堺化学(株)製塩基性炭酸マグネシウム)
SU1:界面活性剤(理研ビタミン(株)製O71D)
SU2:界面活性剤(花王(株)製ポリオキシエチレンジステアレート)
SU3:界面活性剤(三洋化成(株)製ケミスタット3033)
SU4:界面活性剤(クラリアントジャパン(株)Hostapur SAS93)
SU5:界面活性剤(純正化学(株)製ドデシルベンゼンスルホン酸ナトリウム)
熱可塑性樹脂としてLD1、滑剤としてAB1、界面活性剤としてSU1を表1に示す割合で含む組成物を、あらかじめタンブラーブレンダーを用いて5分間予備混合し、得られた混合物を二軸押出機によって混錬した。混練には二軸押出機(東芝機械(株)製TEM26SS)を使用し、押出温度240℃、押出レート20kg/時間の条件で行った。
このようにして得られた溶融混練物をストランド状に押し出し、水冷してからストランドカッターにて切断し、ペレット状の洗浄剤組成物を得た。
得られた洗浄剤組成物について、評価結果を表1に示す。
組成を表1に示すように変更したこと以外は実施例1と同様にして、ペレット状の洗浄剤組成物を得た。
得られた洗浄剤組成物について、評価結果を表1に示す。
[比較例1~9]
組成を表2に示すように変更したこと以外は実施例1と同様にして、ペレット状の洗浄剤組成物を得た。
得られた洗浄剤組成物について、評価結果を表2に示す。
一方で、上記の結果から、比較例1~9で得られた洗浄剤組成物は、分岐指数が低く、洗浄力が十分でないため、洗浄に適さないことが分かった。
2:バレル
3:圧力計
4:ロングダイス
5:ショートダイス
Claims (7)
- 長鎖分岐構造を有する熱可塑性樹脂を含み、絶対分子量100万における分岐指数が0.30超1.00未満であることを特徴とする、成形機用洗浄剤。
- せん断速度100sec-1における190℃の伸長粘度の、せん断速度100sec-1における190℃のせん断粘度に対する割合(伸長粘度/せん断粘度)が30以上である、請求項1に記載の成形機用洗浄剤。
- せん断速度100sec-1における190℃の伸長粘度が42~150kPa・sであり、且つせん断速度100sec-1における190℃のせん断粘度が500~1400Pa・sである、請求項1又は2に記載の成形機用洗浄剤。
- 前記長鎖分岐構造を有する熱可塑性樹脂を5質量%以上70質量%以下含む、請求項1~3のいずれか一項に記載の成形機用洗浄剤。
- 角速度100rad/secにおける190℃の貯蔵弾性率が80kPa以上である、請求項1~4のいずれか一項に記載の成形機用洗浄剤。
- スクラブ効果を有する添加剤の含有量が9質量%以下である、請求項1~5のいずれか一項に記載の成形機用洗浄剤。
- 融点が130℃以上の熱可塑性樹脂を含む、請求項1~6のいずれか一項に記載の成形機用洗浄剤。
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