WO2018150837A1 - Resin cleaning agent and method for melt molding polyester resin - Google Patents

Resin cleaning agent and method for melt molding polyester resin Download PDF

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Publication number
WO2018150837A1
WO2018150837A1 PCT/JP2018/002226 JP2018002226W WO2018150837A1 WO 2018150837 A1 WO2018150837 A1 WO 2018150837A1 JP 2018002226 W JP2018002226 W JP 2018002226W WO 2018150837 A1 WO2018150837 A1 WO 2018150837A1
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WO
WIPO (PCT)
Prior art keywords
resin
polyester resin
compound
cleaning agent
molding
Prior art date
Application number
PCT/JP2018/002226
Other languages
French (fr)
Japanese (ja)
Inventor
鈴木　正章
Original Assignee
日東化工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017024816A external-priority patent/JP6326157B1/en
Priority claimed from JP2017024817A external-priority patent/JP6326158B1/en
Priority claimed from JP2017044050A external-priority patent/JP6326162B1/en
Priority claimed from JP2017044051A external-priority patent/JP6326163B1/en
Application filed by 日東化工株式会社 filed Critical 日東化工株式会社
Priority to CN201880010871.8A priority Critical patent/CN110268016B/en
Priority to KR1020197023049A priority patent/KR20190111982A/en
Publication of WO2018150837A1 publication Critical patent/WO2018150837A1/en

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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/70—Maintenance
    • B29C33/72—Cleaning
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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

Definitions

  • the present invention relates to a resin cleaning agent and a method for melt-molding a polyester resin, and more particularly to a resin cleaning agent used for cleaning inside molding processing equipment such as an extruder and injection molding equipment.
  • thermoplastic resin molding for example, the inside of the molding machine is cleaned when the raw material resin material is changed or the color is changed. Thereby, for example, in the case of material change, the residue of the previously used material can be efficiently discharged.
  • the inside of the molding apparatus is also cleaned to remove carbides and ensure product quality.
  • thermoplastic resin compositions are known as the above resin cleaning agents (Patent Document 1). “(A) 100 parts by mass of polypropylene, (B) 0 to 50 parts by weight of a thermoplastic resin that is not compatible with the component (A) (C) 0.5 to 50 parts by mass of thermoplastic resin for compatibilizing components (A) and (B), and (D) one or more selected from anionic surfactants and nonionic surfactants A cleaning thermoplastic resin composition comprising 0.5 to 15 parts by mass of a surfactant mixture containing one or more of the above. "
  • washing thermoplastic resin composition improves the drawbacks of many previously proposed washing thermoplastic resin compositions, and can be easily replaced with polypropylene when polypropylene is subsequently molded after washing. It is said that there are advantages.
  • An object of the present invention is to provide a novel resin cleaning agent used for cleaning the inside of a molding apparatus using a polyester resin as a raw material resin.
  • the gist of the present invention is a resin cleaning agent used for cleaning the inside of a molding apparatus using a polyester resin as a raw material resin, and a compound capable of forming an ester bond by reacting with a terminal carboxyl group of the polyester resin.
  • the resin cleaning agent is characterized by comprising a melt-mixed product with a polyester resin.
  • another gist of the present invention is that in the melt molding method of polyester resin, when the same molding machine is used and the switching operation is performed by changing the conditions, the polyester resin reacts with the terminal carboxyl group of the polyester resin prior to the switching operation.
  • the polyester resin is melted by introducing a compound capable of forming an ester bond into a molding machine, generating a resin detergent consisting of a melt-mixed product with the polyester resin remaining in the molding machine, and discharging it from the molding machine. Lies in the molding method.
  • a in the general formula (1) is a hydrogen atom
  • BCF biscresol fluorene
  • a in the chemical formula (1) is a hydrogen atom, a methyl group, or an alkyl group having any carbon number, for example, a lower group having 6 or less carbon atoms. It may be an alkyl group or a polyethylene chain. These may have a linear structure or a branched structure. Easily available are BPFL or BCF.
  • the polyethylene chain can be obtained, for example, by addition polymerization of polyethylene to the methyl group of BCF.
  • the compound having the fluorene skeleton represented by the general formula (1) is excellent in heat resistance because of the skeleton.
  • the compound having two or more oxazoline groups in the molecule is not particularly limited, but 2′-methylenebis (2-oxazoline), 2,2′-ethenebis (2-oxazoline), 2,2′-ethenebis (4 -Methyl-2-oxazoline), 2,2′-propenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2, 2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p (phenylenebis (4-phenyl-2-oxazoline), and the like.
  • an oxazoline group-containing polymer can also be used.
  • the oxazoline group-containing polymer can be obtained by polymerizing an addition polymerizable oxazoline such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. Other monomers may be copolymerized as necessary.
  • the polymerization method of the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be employed.
  • oxazoline group-containing polymer examples include EPOCROSS series manufactured by Nippon Shokubai Co., Ltd. Specifically, water-soluble type “WS-500”, “WS-700”, solid type “RPS-1005” Or the like.
  • the compound having two or more epoxy groups in the molecule is not particularly limited.
  • various compounds other than glycidyl ether type epoxy compounds and alicyclic epoxy compounds can be used.
  • glycidyl ether type epoxy compounds include di- or polyglycidyl ethers of polyhydric phenols having an aromatic nucleus or alkylene oxide adducts thereof, di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and the like. Is mentioned.
  • di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, bisphenol fluorene, and alkylene oxide adducts of these phenols ethylene glycol, Diglycidyl ethers of alkylene glycols such as propylene glycol, 1,4-butanediol, 1,6-hexanediol and alkylene oxide adducts thereof; diglycidyl ethers of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; neopentyl glycol; Dibromoneopentyl glycol or diglycidyl ether of alkylene oxide adducts of these glycols; trimethylolethane, trimethyl Di- or triglycidyl ethers of roll propane and glycerin or alkylene oxide adducts of these trihydric alcohols; poly
  • Examples of the alicyclic epoxy compound include cyclohexene oxide obtained by epoxidizing a compound having a cycloalkane ring such as cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide and peracid. And cyclopentene oxide-containing compounds.
  • Examples of commercially available products of pentaerythritol polyglycidyl ether include, for example, trade name “Denacol EX-411” manufactured by Nagase ChemteX Corporation, and examples of commercially available products of diglycerol polyglycidyl ether include those manufactured by Nagase Chemtex Corporation.
  • the name ⁇ Dena Examples of commercially available products of glycerol polyglycidyl ether such as “Role EX-421” include, for example, trade names “Denacol EX-313” and “Denacol EX-314” manufactured by Nagase ChemteX Corporation, such as trimethylolpropane polyglycidyl ether.
  • Examples of commercially available products include, for example, the trade name “Denacol EX-321” manufactured by Nagase ChemteX Corporation, and the commercial name of Neopentylglycol diglycidyl ether such as “Denacol EX-211” manufactured by Nagase ChemteX Corporation.
  • a commercially available product of 1,6-hexanediol diglycidyl ether for example, trade name “Denacol EX-212” manufactured by Nagase ChemteX Corporation
  • a commercially available product of ethylene glycol diglycidyl ether is, for example, Nagase Product name "Denacol” manufactured by Chemtex
  • diethylene glycol diglycidyl ethers such as “X-810” and “Denacol EX-811” include, for example, trade names “Denacol EX-850” and “Denacol EX-851” manufactured by Nagase ChemteX Corporation
  • Commercially available products of diglycidyl ether include, for example, trade names “Denacol EX-821”, “Denacol EX-830”, “Denacol EX-832”, “Denacol EX-841”, “Denacol EX” manufactured by Nagase Chemte
  • epoxy group-containing polymers can also be used.
  • an epoxy group-containing polymer in which an epoxy group is bonded to the main chain of a graft copolymer having a polyolefin as a main chain and a vinyl polymer as a side chain to form a glycidyl group “Modiper A4100”, “Modiper A4300”, “Modiper A4400” and the like can be mentioned.
  • the compound having an acid anhydride group is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, and phthalic anhydride.
  • a compound having two or more acid anhydride groups in the molecule polybasic acid anhydride
  • biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride examples thereof include aliphatic or aromatic tetrabasic acid dianhydrides such as cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and diphenylsulfone tetracarboxylic dianhydride.
  • a polymer having an acid anhydride group can also be used.
  • the polymer having an acid anhydride group is obtained by (co) polymerizing maleic anhydride.
  • acid anhydride group-containing polymers can also be used.
  • commercial products of a copolymer of ⁇ -olefin and maleic anhydride include “Diacarna”, “Modic F532”, “Modic F534A”, etc., manufactured by Mitsubishi Chemical Corporation. It is known as a maleic anhydride-modified polyolefin obtained by graft copolymerization of maleic anhydride.
  • the resin detergent of the present invention comprises a melt-mixed product of a polyester resin and a compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond.
  • the polyester resin used as the base material for the resin cleaner is a general-purpose polyester resin. For example, in the case of cleaning the inside of a molding apparatus performed when changing the raw material resin material, it is usually used after the cleaning. A polyester resin is selected.
  • the polyester resin may be a homopolyester or a copolyester.
  • a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
  • the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • Typical polyester includes polyethylene terephthalate and the like.
  • the dicarboxylic acid component includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.)
  • the glycol component one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like can be mentioned.
  • the compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is not limited to the above-mentioned compounds, and as other examples, for example, isocyanate compounds and carbodiimide compounds can be used. These compounds are also known as crosslinkers.
  • the amount of the compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the ratio of the base polyester resin.
  • additives described in Patent Document 1 for example, various surfactants, metal salts, inorganic fillers, organic phosphorus compounds, and the like can be blended.
  • a lubricant, an antistatic agent, and the like can also be blended.
  • the amount of these additives is appropriately selected, but is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the base polyester resin.
  • the resin cleaning agent of the present invention is generally produced as follows. That is, each of the above components is premixed by a mixer such as a Henschel mixer, a tumbler blender, or a kneader and then melt mixed.
  • the melt mixing process is performed using an extruder, a heating roll, or a Banbury mixer. Usually, it is formed into pellets by melt mixing with an extruder.
  • the size is appropriately selected in consideration of the size of the feed zone of an extruder, an injection molding machine, or the like. What is necessary is just to employ
  • the resin cleaning agent of the present invention is used for cleaning the inside of a molding processing apparatus that uses a polyester resin as a raw material resin, and since the polyester resin is used as a base material, the polyester resin is used in the molding processing apparatus. There is also a great advantage that no different resin is mixed, that is, there is no resin contamination accompanying cleaning of the inside of the molding apparatus.
  • the compatibilizing agent used in the invention described in Patent Document 1 is a case in which when a polymer (polymer alloy) in which two kinds of polymer materials are mixed is made, the polymers cause phase separation and do not mix uniformly. It is an additive used and an additive for forming a copolymer of two kinds of polymers.
  • the hydroxyl group (—OH) of the compound (A), the oxazoline group of the compound (B), the epoxy group of the compound (C), or the (D ) And the terminal carboxyl group (—COOH) of the substrate PET (a) react to form an ester bond. And relative viscosity falls by formation of a branched structure.
  • a small amount of water is generated by the dehydration reaction due to heat during the melt mixing process and the ester bond is hydrolyzed, the total amount of the reactive groups of the respective compounds is not lost.
  • the resin detergent of the present invention moves while being melt-mixed with the polyester resin adhering to and remaining in the molding apparatus by the same melt-mixing treatment as described above.
  • the flow of the resin cleaning agent of the present invention inside the molding apparatus is good with a reduced viscosity as compared with the substrate PET (a) alone, and exhibits a high cleaning effect.
  • the reactive group of each compound reacts with the terminal carboxyl group (—COOH) of PET (b) adhering / remaining inside the molding apparatus to form an ester bond.
  • a branched structure is formed, the relative viscosity is further reduced, and the discharge from the inside of the molding apparatus becomes easier.
  • molding processing apparatus is also contained in said carboxyl group.
  • a of the compound having a fluorene skeleton represented by the general formula (1) is an alkyl group or a polyethylene chain
  • a resin detergent having improved heat resistance can be obtained as follows. That is, polystyrene is used together with the base polyester resin in the production of the resin detergent, and the base polyester resin and polystyrene are copolymerized with a hydroxyl group and an alkyl group or a polyethylene chain, thereby increasing the heat resistance of the base polyester resin. .
  • polystyrene since polystyrene has the property that it does not yellow or burn black at high temperatures, it can cover these drawbacks of polyester resins that gel, yellow or burn black at high temperatures.
  • the resin detergent of the present invention is used in the following various modes.
  • a melt-mixed product of a compound capable of reacting with a terminal carboxyl group of a polyester resin to form an ester bond and a polyester resin is produced in advance and used as, for example, pellets. This embodiment is suitable for commercializing the resin detergent of the present invention.
  • polyester resin melt molding method of the present invention forms an ester bond by reacting with the terminal carboxyl group of the polyester resin prior to the switching operation when changing the conditions using the same molding machine.
  • This is a polyester resin melt-molding method characterized in that a compound cleaning agent made of a melt-mixed product with a polyester resin remaining inside is injected into a molding machine and discharged from the molding machine.
  • the compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the polyester resin remaining in the molding machine. is there.
  • the amount of the remaining polyester resin can be easily measured as the retention amount in the molding machine.
  • examples of the molding machine include an extrusion molding machine and an injection molding machine.
  • a mode of changing the conditions a case where the resin colorant and other additives are changed is representative, but there is also a case where the conditions are changed to a polyester resin having a different intrinsic viscosity.
  • Production Example 1 10 parts by weight of biscresol fluorene (BCF) (manufactured by JFE Chemical) was added to 100 parts by weight of a polyester resin (Mitsubishi Chemical product “NOVAPEX” G2 grade (intrinsic viscosity: 0.59 dL / g) and premixed with a mixer. Thereafter, the mixture was kneaded with an extruder and injection molded in the manner described below to obtain a pellet-shaped resin cleaning agent (A) having a diameter of 3 mm and a length of 3 mm. Polyester resin pellets containing no BCF were also produced.
  • BCF biscresol fluorene
  • Extrusion conditions Extrusion conditions
  • Extruder “PCM45” (screw diameter 46 mm) manufactured by Ikegai Co., Ltd.
  • Injection conditions Screw rotation speed 184rpm Temperature condition: 300 ° C (Injection molding conditions) Injection molding machine; “M-100C” manufactured by Meiki Seisakusho Co., Ltd.
  • Injection conditions Screw rotation speed 80rpm, injection speed 50%, injection pressure 10MPA, back pressure 0MPA Temperature condition: 290 ° C
  • Production Example 2 A pellet was produced in the same manner as in Production Example 1 except that 10 parts by weight of an oxazoline group-containing polymer (“Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.) was used instead of biscresol fluorene (BCF) in Production Example 1. A shaped resin cleaner (B) was obtained.
  • an oxazoline group-containing polymer (“Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.) was used instead of biscresol fluorene (BCF) in Production Example 1.
  • BCF biscresol fluorene
  • Production Example 3 A pellet-shaped resin was produced in the same manner as in Production Example 1 except that 10 parts by weight of an epoxy group-containing polymer (“Modiper A4400” manufactured by NOF) was used instead of biscresol fluorene (BCF) in Production Example 1. A cleaning agent (C) was obtained.
  • an epoxy group-containing polymer (“Modiper A4400” manufactured by NOF”
  • BCF biscresol fluorene
  • Production Example 4 In Production Example 1, pellets were prepared in the same manner as in Production Example 1 except that 1 part by weight of an anhydride group-containing polymer ("Diacanal 30" manufactured by Mitsubishi Chemical Corporation) was used instead of biscresol fluorene (BCF). A resin cleaning agent (D) having a shape was obtained.
  • an anhydride group-containing polymer (“Diacanal 30" manufactured by Mitsubishi Chemical Corporation) was used instead of biscresol fluorene (BCF).
  • BCF biscresol fluorene
  • Example 1 Evaluation of resin cleaner: The extruder and the injection molding machine were washed in the manufacturing process of colored polyester resin pellets employing the same conditions as described above. In the production of the colored polyester resin pellets, the same polyester resin as described above and 10% by weight of a resin colorant (polyester masterbatch turquoise blue manufactured by Nippon Pigment) were used.
  • a resin colorant polyyester masterbatch turquoise blue manufactured by Nippon Pigment
  • the supply to the extruder was switched to the resin detergent pellets (A), and continuous supply was performed until colorless polyester resin pellets were obtained, and the supply amount necessary for cleaning was determined (Example 1). ).
  • the supply to the extruder is switched to polyester resin pellets containing no BCF, and it is continuously supplied until colorless polyester resin pellets are obtained, which is necessary for washing.
  • the supply amount was determined (Comparative Example 1).
  • the supply amount necessary for cleaning in the case of Comparative Example 1 was about twice that of Example 1.
  • Example 1 instead of the resin detergent pellet (A), the resin detergent pellets (B) to (D) were used according to the evaluation results of the resin detergent in the same manner as in Example 1. The same results as in Example 1 were obtained. That is, in Examples 2 to 4, the supply amount necessary for cleaning in Comparative Example 1 was about twice that in Examples 2 to 4.

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Abstract

Provided is a novel resin cleaning agent which is used for the cleaning of the inside of a molding apparatus that uses a polyester resin as a starting material resin. A resin cleaning agent which is used for the cleaning of the inside of a molding apparatus that uses a polyester resin as a starting material resin, and which is formed from a melt mixed product of a polyester resin and a compound that is capable of forming an ester bond by reacting with a terminal carboxyl group of the polyester resin.

Description

樹脂洗浄剤およびポリエステル樹脂の溶融成形方法Resin cleaner and method for melt molding polyester resin
　本発明は、樹脂洗浄剤およびポリエステル樹脂の溶融成形方法に関し、詳しくは、押出機、射出成形機器などの成形加工機器内部の洗浄に使用する樹脂洗浄剤に関する。 The present invention relates to a resin cleaning agent and a method for melt-molding a polyester resin, and more particularly to a resin cleaning agent used for cleaning inside molding processing equipment such as an extruder and injection molding equipment.
　熱可塑性樹脂の成形加工の分野においては、例えば、原料樹脂材料換え、色換えの際、成形加工機器内部の洗浄が行われる。これにより、例えば、材料換えの場合は、前に使用した材料の残留物の排出を効率的に行うことが出来る。また、成形加工機器内部の洗浄は、炭化物を除去して製品品質を確保するためにも行われる。 In the field of thermoplastic resin molding, for example, the inside of the molding machine is cleaned when the raw material resin material is changed or the color is changed. Thereby, for example, in the case of material change, the residue of the previously used material can be efficiently discharged. In addition, the inside of the molding apparatus is also cleaned to remove carbides and ensure product quality.
　従来、上記のような樹脂洗浄剤としては次のような熱可塑性樹脂組成物が知られている（特許文献１）。
「（Ａ）ポリプロピレン１００質量部に対して、
　（Ｂ）（Ａ）成分と相溶化しない熱可塑性樹脂０～５０質量部、
　（Ｃ）（Ａ）成分及び（Ｂ）成分を相溶化させるための熱可塑性樹脂０．５～５０質量部、及び
　（Ｄ）アニオン界面活性剤から選ばれる１種以上とノニオン界面活性剤から選ばれる１種以上を含む界面活性剤混合物０．５～１５質量部を含有する洗浄用の熱可塑性樹脂組成物。」 Conventionally, the following thermoplastic resin compositions are known as the above resin cleaning agents (Patent Document 1).
“(A) 100 parts by mass of polypropylene,
(B) 0 to 50 parts by weight of a thermoplastic resin that is not compatible with the component (A)
(C) 0.5 to 50 parts by mass of thermoplastic resin for compatibilizing components (A) and (B), and (D) one or more selected from anionic surfactants and nonionic surfactants A cleaning thermoplastic resin composition comprising 0.5 to 15 parts by mass of a surfactant mixture containing one or more of the above. "
　上記の洗浄用熱可塑性樹脂組成物は、既に提案されていた数多くの洗浄用熱可塑性樹脂組成物の欠点を改良すると共に、洗浄後に続いてポリプロピレンを成形する場合にポリプロピレンへの置換が容易であるとの利点があるとされている。 The above-mentioned washing thermoplastic resin composition improves the drawbacks of many previously proposed washing thermoplastic resin compositions, and can be easily replaced with polypropylene when polypropylene is subsequently molded after washing. It is said that there are advantages.
特開２０１２－１４０４８１号公報JP 2012-140481 A
　本発明の目的は、原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用する新規な樹脂洗浄剤を提供することにある。 An object of the present invention is to provide a novel resin cleaning agent used for cleaning the inside of a molding apparatus using a polyester resin as a raw material resin.
　本発明者は、上記の目的を達成すべく鋭意検討した結果、特定の化合物を巧みに利用することにより上記の目的を達成し得るとの知見を得た。 As a result of intensive studies to achieve the above object, the present inventor has obtained knowledge that the above object can be achieved by skillfully using a specific compound.
　すなわち、本発明の要旨は、原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用する樹脂洗浄剤であって、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物とポリエステル樹脂との溶融混合処理物から成ることを特徴とする樹脂洗浄剤に存する。 That is, the gist of the present invention is a resin cleaning agent used for cleaning the inside of a molding apparatus using a polyester resin as a raw material resin, and a compound capable of forming an ester bond by reacting with a terminal carboxyl group of the polyester resin. The resin cleaning agent is characterized by comprising a melt-mixed product with a polyester resin.
　また、本発明の他の要旨は、ポリエステル樹脂の溶融成形方法において、同一の成型機を使用し条件を変更して切替運転を行うに際し、切替運転に先立ち、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物を成型機に投入して内部に残存するポリエステル樹脂との溶融混合処理物から成る樹脂洗浄剤を生成させて成型機から排出させることを特徴とするポリエステル樹脂の溶融成形方法に存する。 In addition, another gist of the present invention is that in the melt molding method of polyester resin, when the same molding machine is used and the switching operation is performed by changing the conditions, the polyester resin reacts with the terminal carboxyl group of the polyester resin prior to the switching operation. The polyester resin is melted by introducing a compound capable of forming an ester bond into a molding machine, generating a resin detergent consisting of a melt-mixed product with the polyester resin remaining in the molding machine, and discharging it from the molding machine. Lies in the molding method.
　そして、本発明の好ましい態様においては、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物としては、以下に記載の一般式（１）で表されるフルオレン骨格を有する化合物（Ａ）、分子内に２個以上のオキサゾリン基を有する化合物（Ｂ）、分子内に２個以上のエポキシ基を有する化合物（Ｃ）、酸無水物基を有する化合物（Ｄ）の群から選択される少なくとも１種の化合物が使用される。 And in the preferable aspect of this invention, as a compound which can react with the terminal carboxyl group of a polyester resin and can form an ester bond, the compound (A which has the fluorene skeleton represented by the following General formula (1) (A) ), A compound (B) having two or more oxazoline groups in the molecule, a compound (C) having two or more epoxy groups in the molecule, and a compound (D) having an acid anhydride group At least one compound is used.
Figure JPOXMLDOC01-appb-C000002
  
Figure JPOXMLDOC01-appb-C000002
  
　本発明によれば前記の目的が達成される。 According to the present invention, the above object is achieved.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
＜樹脂洗浄剤＞
　先ず、前記の一般式（１）で表されるフルオレン骨格を有する化合物（Ａ）について説明する。 <Resin cleaning agent>
First, the compound (A) having a fluorene skeleton represented by the general formula (1) will be described.
　一般式（１）中のＡが水素原子で表される化合物はビスフェノールフルオレン（ＢＰＦＬ）であり、メチル基で表される化合物はビスクレゾールフルオレン（ＢＣＦ）である。これらの化合物は光機能性原料として良く知られている。本発明において、前記の化合物において、２個の水酸基が重要であり、化学式（１）中のＡは、水素原子、メチル基の他、任意の炭素数のアルキル基、例えば炭素数６以下の低級アルキル基であってもよく、ポリエチレン鎖であってもよい。これらは直鎖構造であっても分岐構造であってもよい。容易に入手できるのはＢＰＦＬ又はＢＣＦである。ポリエチレン鎖は例えばＢＣＦのメチル基にポリエチレンを付加重合させることにより得ることが可能である。因に、前記の一般式（１）で表されるフルオレン骨格を有する化合物は、その骨格故に耐熱性に優れる。 The compound in which A in the general formula (1) is a hydrogen atom is bisphenol fluorene (BPFL), and the compound represented by a methyl group is biscresol fluorene (BCF). These compounds are well known as photofunctional raw materials. In the present invention, two hydroxyl groups are important in the above compound, and A in the chemical formula (1) is a hydrogen atom, a methyl group, or an alkyl group having any carbon number, for example, a lower group having 6 or less carbon atoms. It may be an alkyl group or a polyethylene chain. These may have a linear structure or a branched structure. Easily available are BPFL or BCF. The polyethylene chain can be obtained, for example, by addition polymerization of polyethylene to the methyl group of BCF. Incidentally, the compound having the fluorene skeleton represented by the general formula (1) is excellent in heat resistance because of the skeleton.
　次に、分子内に２個以上のオキサゾリン基を有する化合物（Ｂ）について説明する。 Next, the compound (B) having two or more oxazoline groups in the molecule will be described.
　分子内に２個以上のオキサゾリン基を有する化合物は、特に、制限されないが、２´－メチレンビス（２－オキサゾリン）、２，２´－エテンビス（２－オキサゾリン）、２，２´－エテンビス（４－メチル－２－オキサゾリン）、２，２´－プロペンビス（２－オキサゾリン）、２，２´－テトラメチレンビス（２－オキサゾリン）、２，２´－ヘキサメチレンビス（２－オキサゾリン）、２，２´－オクタメチレンビス（２－オキサゾリン）、２，２´－ｐ－フェニレンビス（２－オキサゾリン）、２，２´－ｐ－フェニレンビス（４，４´－ジメチル－２－オキサゾリン）、２，２´－ｐ－フェニレンビス（４－メチル－２－オキサゾリン）、２，２´－ｐ（フェニレンビス（４－フェニル－２－オキサゾリン）等を挙げることができる。 The compound having two or more oxazoline groups in the molecule is not particularly limited, but 2′-methylenebis (2-oxazoline), 2,2′-ethenebis (2-oxazoline), 2,2′-ethenebis (4 -Methyl-2-oxazoline), 2,2′-propenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2, 2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p (phenylenebis (4-phenyl-2-oxazoline), and the like.
　上記の他、オキサゾリン基含有ポリマーも使用することも出来る。オキサゾリン基含有ポリマーは、２－ビニル－２－オキサゾリン、２－ビニル－４－メチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン等の付加重合性オキサゾリンを重合させることにより得られる。必要に応じて他の単量体が共重合されていてもよい。オキサゾリン基含有ポリマーの重合方法は、特に限定されず、公知の種々の重合方法を採用することができる。 In addition to the above, an oxazoline group-containing polymer can also be used. The oxazoline group-containing polymer can be obtained by polymerizing an addition polymerizable oxazoline such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. Other monomers may be copolymerized as necessary. The polymerization method of the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be employed.
  オキサゾリン基含有ポリマーの市販品としては、日本触媒社製のエポクロスシリーズが挙げられ、具体的には、水溶性タイプの「ＷＳ－５００」、「ＷＳ－７００」、固形タイプの「ＲＰＳ－１００５」などが挙げられる。 Commercially available products of the oxazoline group-containing polymer include EPOCROSS series manufactured by Nippon Shokubai Co., Ltd. Specifically, water-soluble type “WS-500”, “WS-700”, solid type “RPS-1005” Or the like.
　次に、分子内に２個以上のエポキシ基を有する化合物（Ｃ）について説明する。 Next, the compound (C) having two or more epoxy groups in the molecule will be described.
　分子内に２個以上のエポキシ基を有する化合物は、特に、制限されないが、例えば、グリシジルエーテル型エポキシ化合物、脂環式エポキシ化合物の他、種々の化合物が使用できる。 The compound having two or more epoxy groups in the molecule is not particularly limited. For example, various compounds other than glycidyl ether type epoxy compounds and alicyclic epoxy compounds can be used.
　グリシジルエーテル型エポキシ化合物としては、例えば、芳香族核を有する多価フェノール類又はそのアルキレンオキサイド付加体のジ又はポリグリシジルエーテル、脂肪族多価アルコール又はそのアルキレンオキサイド付加体のジ又はポリグリシジルエーテル等が挙げられる。具体的には、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、水添ビスフェノールＡ、水添ビスフェノールＦ、水添ビスフェノールＳ、ビスフェノールフルオレン及びこれらフェノール類のアルキレンオキサイド付加体のジ又はポリグリシジルエーテル；エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール及びそのアルキレンオキサイド付加体等のアルキレングリコールのジグリシジルエーテル；ポリエチレングリコール及びポリプロピレングリコール等のポリアルキレングリコールのジグリシジルエーテル；ネオペンチルグリコール、ジブロモネオペンチルグリコール又はこれらグリコールのアルキレンオキサイド付加体のジグリシジルエーテル；トリメチロールエタン、トリメチロールプロパン及びグリセリン又はこれら３価アルコールのアルキレンオキサイド付加体のジ又はトリグリシジルエーテル；ペンタエリスリのジ、トリ又はテトラグリジジルエーテル等の多価アルトール又はそのアルキレンオキサイド付加体コールのポリグリシジルエーテル；ノボラック型エポキシ樹脂；クレゾールノボラック樹脂；並びにこれら化合物の芳香族核がハロゲン置換された化合物等が挙げられる。 Examples of glycidyl ether type epoxy compounds include di- or polyglycidyl ethers of polyhydric phenols having an aromatic nucleus or alkylene oxide adducts thereof, di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and the like. Is mentioned. Specifically, di- or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, bisphenol fluorene, and alkylene oxide adducts of these phenols; ethylene glycol, Diglycidyl ethers of alkylene glycols such as propylene glycol, 1,4-butanediol, 1,6-hexanediol and alkylene oxide adducts thereof; diglycidyl ethers of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; neopentyl glycol; Dibromoneopentyl glycol or diglycidyl ether of alkylene oxide adducts of these glycols; trimethylolethane, trimethyl Di- or triglycidyl ethers of roll propane and glycerin or alkylene oxide adducts of these trihydric alcohols; polyaltidyls such as pentaerythritol di-, tri- or tetraglycidyl ethers or polyglycidyl ethers of alkylene oxide adducts thereof; novolac type Examples thereof include epoxy resins; cresol novolac resins; and compounds in which the aromatic nucleus of these compounds is substituted with halogen.
　脂環式エポキシ化合物としては、例えば、シクロへキセン又はシクロペンテン環等のシクロアルカン環を有する化合物を、過酸化水素及び過酸等の適当な酸化剤でエポキシ化することによって得られる、シクロヘキセンオキサイド又はシクロペンテンオキサイド含有化合物等が挙げられる。具体的には、３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－メタ－ジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ビニルシクロヘキセンオキサイド、４－ビニルエポキシシクロヘキサン、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキシル－３’，４’－エポキシ－６’－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、ジシクロペンタジエンジエポキサイド、エチレングリコールのジ（３，４－エポキシシクロヘキシルメチル）エーテル、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシ化テトラベンジルアルコール、ラクトン変性３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、ラクトン変性エポキシ化テトラヒドロベンジルアルコール、シクロヘキセンオキサイド等が挙げられる。 Examples of the alicyclic epoxy compound include cyclohexene oxide obtained by epoxidizing a compound having a cycloalkane ring such as cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide and peracid. And cyclopentene oxide-containing compounds. Specifically, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta- Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl -3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, Renbis (3,4-epoxycyclohexanecarboxylate), epoxidized tetrabenzyl alcohol, lactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, lactone-modified epoxidized tetrahydrobenzyl alcohol, cyclohexene oxide, etc. Is mentioned.
　分子内に２個以上のエポキシ基を有する化合物は数多くのものが市販されており容易に入手することが出来る。例えば、ビスフェノールＡ・エピクロルヒドリン型のエポキシ樹脂、ソルビトールポリグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－６１１」、「デナコールＥＸ－６１２」、「デナコールＥＸ－６１４」、「デナコールＥＸ－６１４Ｂ」、「デナコールＥＸ－６２２」等、ポリグリセロールポリグリシジルエーテルの市販品としては、ナガセケムテックス社製の商品名「デナコールＥＸ－５１２」、「デナコールＥＸ－５２１」等、ペンタエリスリトールポリグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－４１１」等、ジグリセロールポリグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－４２１」等、グリセロールポリグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－３１３」、「デナコールＥＸ－３１４」等、トリメチロールプロパンポリグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－３２１」等、ネオペンチルグリコールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－２１１」等、１，６－ヘキサンジオールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－２１２」等、エチレングリコールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－８１０」、「デナコールＥＸ－８１１」等、ジエチレングリコールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－８５０」、「デナコールＥＸ－８５１」等、ポリエチレングリコールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－８２１」、「デナコールＥＸ－８３０」、「デナコールＥＸ－８３２」、「デナコールＥＸ－８４１」、「デナコールＥＸ－８６１」等、プロピレングリコールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－９１１」等、ポリプロピレングリコールジグリシジルエーテルの市販品としては、例えば、ナガセケムテックス社製の商品名「デナコールＥＸ－９４１」、「デナコールＥＸ－９２０」、「デナコールＥＸ－９３１」等、ジグリシジルアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン等が挙げられる。 Many compounds having two or more epoxy groups in the molecule are commercially available and can be easily obtained. For example, commercially available products of bisphenol A / epichlorohydrin type epoxy resin and sorbitol polyglycidyl ether include, for example, trade names “Denacol EX-611”, “Denacol EX-612”, “Denacol EX-614” manufactured by Nagase ChemteX Corporation. ”,“ Denacol EX-614B ”,“ Denacol EX-622 ”, and other commercial products of polyglycerol polyglycidyl ether include trade names“ Denacol EX-512 ”,“ Denacol EX-521 ”, etc., manufactured by Nagase ChemteX Corporation. Examples of commercially available products of pentaerythritol polyglycidyl ether include, for example, trade name “Denacol EX-411” manufactured by Nagase ChemteX Corporation, and examples of commercially available products of diglycerol polyglycidyl ether include those manufactured by Nagase Chemtex Corporation. The name `` Dena Examples of commercially available products of glycerol polyglycidyl ether such as “Role EX-421” include, for example, trade names “Denacol EX-313” and “Denacol EX-314” manufactured by Nagase ChemteX Corporation, such as trimethylolpropane polyglycidyl ether. Examples of commercially available products include, for example, the trade name “Denacol EX-321” manufactured by Nagase ChemteX Corporation, and the commercial name of Neopentylglycol diglycidyl ether such as “Denacol EX-211” manufactured by Nagase ChemteX Corporation. As a commercially available product of 1,6-hexanediol diglycidyl ether, for example, trade name “Denacol EX-212” manufactured by Nagase ChemteX Corporation, for example, a commercially available product of ethylene glycol diglycidyl ether is, for example, Nagase Product name "Denacol" manufactured by Chemtex Examples of commercially available diethylene glycol diglycidyl ethers such as “X-810” and “Denacol EX-811” include, for example, trade names “Denacol EX-850” and “Denacol EX-851” manufactured by Nagase ChemteX Corporation, polyethylene glycol Commercially available products of diglycidyl ether include, for example, trade names “Denacol EX-821”, “Denacol EX-830”, “Denacol EX-832”, “Denacol EX-841”, “Denacol EX” manufactured by Nagase ChemteX Corporation. Commercially available products of propylene glycol diglycidyl ether such as “-861” and the like, for example, commercial names of polypropylene glycol diglycidyl ether such as “Denacol EX-911” manufactured by Nagase ChemteX Corporation, such as Nagase ChemteX, Inc. Product name " Denacol EX-941, Denacol EX-920, Denacol EX-931, etc., diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N , N′-diglycidylaminomethyl) cyclohexane and the like.
　エポキシ基含有ポリマーの市販品も使用することが出来る。例えば、ポリオレフィンを主鎖とし、ビニル系ポリマーを側鎖とするグラフトコポリマーの主鎖にエポキシ基が結合してグリシジル基を形成したエポキシ基含有ポリマーの市販品としては、日油社製の商品名「モディパーＡ４１００」、「モディパーＡ４３００」「モディパーＡ４４００」等が挙げられる。 Commercial products of epoxy group-containing polymers can also be used. For example, as a commercial product of an epoxy group-containing polymer in which an epoxy group is bonded to the main chain of a graft copolymer having a polyolefin as a main chain and a vinyl polymer as a side chain to form a glycidyl group, “Modiper A4100”, “Modiper A4300”, “Modiper A4400” and the like can be mentioned.
　次に、酸無水物基を有する化合物（Ｄ）について説明する。 Next, the compound (D) having an acid anhydride group will be described.
　酸無水物基を有する化合物は、特に、制限されないが、例えば、無水コハク酸、無水マレイン酸、無水フタル酸などを挙げることができる。また、分子内に２個以上の酸無水物基を有する化合物（多塩基酸無水物）としては、ビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ジフェニルスルホンテトラカルボン酸二無水物等の脂肪族あるいは芳香族四塩基酸二無水物などが挙げられる。 The compound having an acid anhydride group is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, and phthalic anhydride. In addition, as a compound having two or more acid anhydride groups in the molecule (polybasic acid anhydride), biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, Examples thereof include aliphatic or aromatic tetrabasic acid dianhydrides such as cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and diphenylsulfone tetracarboxylic dianhydride.
　上記の他、酸無水物基を有するポリマーも使用することが出来る。酸無水物基を有するポリマーは無水マレイン酸を（共）重合して得られる。 In addition to the above, a polymer having an acid anhydride group can also be used. The polymer having an acid anhydride group is obtained by (co) polymerizing maleic anhydride.
　酸無水物基含有ポリマーの市販品も使用することが出来る。例えば、α－オレフィンと無水マレイン酸の共重合体の市販品としては、三菱化学社製の商品名「ダイヤカルナ」、「モデイックＦ５３２」、「モデイックＦ５３４Ａ」等が挙げられる。無水マレイン酸をグラフト共重合した無水マレイン酸変性ポリオレフィンとして知られている。例えば、三洋化成工業社製の商品「ユーメックス２０００」等がある。 Commercial products of acid anhydride group-containing polymers can also be used. For example, commercial products of a copolymer of α-olefin and maleic anhydride include “Diacarna”, “Modic F532”, “Modic F534A”, etc., manufactured by Mitsubishi Chemical Corporation. It is known as a maleic anhydride-modified polyolefin obtained by graft copolymerization of maleic anhydride. For example, there is a product “Yumex 2000” manufactured by Sanyo Chemical Industries.
　本発明の樹脂洗浄剤は、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物とポリエステル樹脂との溶融混合処理物から成る。樹脂洗浄剤の基材として使用されるポリエステル樹脂は、汎用のポリエステル樹脂であり、例えば、原料樹脂材料換えの際に行われる成形加工機器内部の洗浄の場合は、通常、洗浄後に続いて使用するポリエステル樹脂が選択される。 The resin detergent of the present invention comprises a melt-mixed product of a polyester resin and a compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond. The polyester resin used as the base material for the resin cleaner is a general-purpose polyester resin. For example, in the case of cleaning the inside of a molding apparatus performed when changing the raw material resin material, it is usually used after the cleaning. A polyester resin is selected.
　前記のポリエステル樹脂はホモポリエステルであっても共重合ポリエステルであってもよい。ホモポリエステルの場合、芳香族ジカルボン酸と脂肪族グリコールとを重縮合させて得られるものが好ましい。芳香族ジカルボン酸としては、テレフタル酸、２，６－ナフタレンジカルボン酸などが挙げられ、脂肪族グリコールとしては、エチレングリコール、ジエチレングリコール、１，４－シクロヘキサンジメタノール等が挙げられる。代表的なポリエステルとしては、ポリエチレンテレフタレート等が例示される。一方、共重合ポリエステルの場合、ジカルボン酸成分としては、イソフタル酸、フタル酸、テレフタル酸、２，６－ナフタレンジカルボン酸、アジピン酸、セバシン酸、オキシカルボン酸（例えば、ｐ－オキシ安息香酸など）等の一種または二種以上が挙げられ、グリコール成分として、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブタンジオール、４－シクロヘキサンジメタノール、ネオペンチルグリコール等の一種または二種以上が挙げられる。 The polyester resin may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical polyester includes polyethylene terephthalate and the like. On the other hand, in the case of a copolyester, the dicarboxylic acid component includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.) As the glycol component, one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like can be mentioned.
　ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物は、前記の化合物に限定されず、他の例としては、例えば、イソシアネート系化合物、カルボジイミド系化合物なども使用可能である。これらの化合物は、架橋剤としても知られている。 The compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is not limited to the above-mentioned compounds, and as other examples, for example, isocyanate compounds and carbodiimide compounds can be used. These compounds are also known as crosslinkers.
　ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物の使用量は、基材ポリエステル樹脂に対する割合として、通常１～３０重量％、好ましくは５～２０重量％である。 The amount of the compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the ratio of the base polyester resin.
　本発明においては、前述の特許文献１に記載の添加剤、例えば、各種の界面活性剤、金属塩、無機フィラー、有機燐化合物などを配合することが出来る。上記の他、滑剤、帯電防止剤なども配合することが出来る。これらの添加剤の配合量は、適宜選択されるが、基材ポリエステル樹脂に対する割合として、通常１～３０重量％、好ましくは５～２０重量％である。 In the present invention, additives described in Patent Document 1, for example, various surfactants, metal salts, inorganic fillers, organic phosphorus compounds, and the like can be blended. In addition to the above, a lubricant, an antistatic agent, and the like can also be blended. The amount of these additives is appropriately selected, but is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the base polyester resin.
　本発明の樹脂洗浄剤は一般的には次の様にして製造される。すなわち、前記各成分を、ヘンシェルミキサー、タンブラーブレンダー、ニーダー等の混合機で予備混合した後に溶融混合処理する。溶融混合処理は、押出機や、加熱ロール、バンバリーミキサーを使用して行われる。通常、押出機で溶融混合処理してペレット形状に成形される。その大きさは、押出機、射出成形機器などのフィドゾーンの大きさを考慮して適宜選択される。押出機での溶融混合処理の条件は、ポリエステル樹脂ペレットの製造条件として知られている公知の条件を採用すればよい。 The resin cleaning agent of the present invention is generally produced as follows. That is, each of the above components is premixed by a mixer such as a Henschel mixer, a tumbler blender, or a kneader and then melt mixed. The melt mixing process is performed using an extruder, a heating roll, or a Banbury mixer. Usually, it is formed into pellets by melt mixing with an extruder. The size is appropriately selected in consideration of the size of the feed zone of an extruder, an injection molding machine, or the like. What is necessary is just to employ | adopt the well-known conditions known as manufacturing conditions of a polyester resin pellet as the conditions of the melt mixing process in an extruder.
　本発明の樹脂洗浄剤は、原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用するものであり、しかも、基材としてポリエステル樹脂を使用しているため、成形加工機器内にポリエステル樹脂と異なる樹脂が混入されることがない、すなわち、成形加工機器内部の洗浄に伴う樹脂のコンタミが全くないという大きな利点もある。 The resin cleaning agent of the present invention is used for cleaning the inside of a molding processing apparatus that uses a polyester resin as a raw material resin, and since the polyester resin is used as a base material, the polyester resin is used in the molding processing apparatus. There is also a great advantage that no different resin is mixed, that is, there is no resin contamination accompanying cleaning of the inside of the molding apparatus.
　特許文献１記載発明で使用されている相溶化剤は、２種類の高分子材料を混合した樹脂（ポリマアロイ）を作ろうとした際に高分子同士が相分離を起こして均一に混ざり合わない場合に使用される添加剤であり、２種類の高分子の共重合体を形成するための添加剤のことである。 The compatibilizing agent used in the invention described in Patent Document 1 is a case in which when a polymer (polymer alloy) in which two kinds of polymer materials are mixed is made, the polymers cause phase separation and do not mix uniformly. It is an additive used and an additive for forming a copolymer of two kinds of polymers.
　従って、本発明の樹脂洗浄剤で使用する前記の各化合物の作用効果は、従来の相溶化剤とは異なり、次の様に推定される。 Therefore, unlike the conventional compatibilizer, the action and effect of each compound used in the resin detergent of the present invention is estimated as follows.
　本発明の樹脂洗浄剤の製造時、溶融混合処理により、化合物（Ａ）の水酸基（－ＯＨ）、化合物の（Ｂ）のオキサゾリン基、化合物の（Ｃ）のエポキシ基、または、化合物の（Ｄ）の酸無水物基と基材ＰＥＴ（ａ）の末端カルボキシル基（－ＣＯＯＨ）とが反応してエステル結合を形成する。そして、分岐構造の形成により相対粘度が低下する。勿論、溶融混合処理時の熱による脱水反応により少量の水が生成してエステル結合が加水分解されるため、前記の各化合物の反応性基の全量が消失することはない。 During the production of the resin detergent of the present invention, the hydroxyl group (—OH) of the compound (A), the oxazoline group of the compound (B), the epoxy group of the compound (C), or the (D ) And the terminal carboxyl group (—COOH) of the substrate PET (a) react to form an ester bond. And relative viscosity falls by formation of a branched structure. Of course, since a small amount of water is generated by the dehydration reaction due to heat during the melt mixing process and the ester bond is hydrolyzed, the total amount of the reactive groups of the respective compounds is not lost.
　本発明の樹脂洗浄剤の使用時、前記と同様の溶融混合処理により、樹脂洗浄剤は、成形加工機器内部に付着・残留するポリエステル樹脂と溶融混合されつつ移動する。本発明の樹脂洗浄剤の成形加工機器内部の流れは、基材ＰＥＴ（ａ）単独に比し、粘度が低下して良好であり、高い洗浄効果を発揮する。そして、前記の各化合物の反応性基と成形加工機器内部に付着・残留するＰＥＴ（ｂ）の末端カルボキシル基（－ＣＯＯＨ）とが反応（架橋反応）してエステル結合を形成する。この際、前記と同様、分岐構造が形成され、相対粘度は一層低下し、成形加工機器内部からの排出が一層容易となる。なお、上記のカルボキシル基には成形加工機器内部での分解反応によって生じたものも含まれる。 When the resin detergent of the present invention is used, the resin detergent moves while being melt-mixed with the polyester resin adhering to and remaining in the molding apparatus by the same melt-mixing treatment as described above. The flow of the resin cleaning agent of the present invention inside the molding apparatus is good with a reduced viscosity as compared with the substrate PET (a) alone, and exhibits a high cleaning effect. Then, the reactive group of each compound reacts with the terminal carboxyl group (—COOH) of PET (b) adhering / remaining inside the molding apparatus to form an ester bond. At this time, as described above, a branched structure is formed, the relative viscosity is further reduced, and the discharge from the inside of the molding apparatus becomes easier. In addition, what was produced by the decomposition reaction inside a shaping | molding processing apparatus is also contained in said carboxyl group.
　なお、前記の一般式（１）で表されるフルオレン骨格を有する化合物のＡがアルキル基またはポリエチレン鎖の場合は、次のようにして耐熱性の改良された樹脂洗浄剤を得ることも出来る。すなわち、樹脂洗浄剤の製造の際に基材ポリエステル樹脂と共にポリスチレンを使用し、水酸基とアルキル基またはポリエチレン鎖により、基材ポリエステル樹脂とポリスチレンとを共重合させ、基材ポリエステル樹脂の耐熱性を高める。具体的には、ポリスチレンは、高温で黄変したり黒色に焼けたりしない特性があるため、高温ではゲル化したり黄変したり黒色に焼けるポリエステル樹脂のこれらの欠点をカバーすることが出来る。 In addition, when A of the compound having a fluorene skeleton represented by the general formula (1) is an alkyl group or a polyethylene chain, a resin detergent having improved heat resistance can be obtained as follows. That is, polystyrene is used together with the base polyester resin in the production of the resin detergent, and the base polyester resin and polystyrene are copolymerized with a hydroxyl group and an alkyl group or a polyethylene chain, thereby increasing the heat resistance of the base polyester resin. . Specifically, since polystyrene has the property that it does not yellow or burn black at high temperatures, it can cover these drawbacks of polyester resins that gel, yellow or burn black at high temperatures.
　本発明の樹脂洗浄剤は以下のような各種の態様で使用される。
（１）ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物とポリエステル樹脂との溶融混合処理物を予め製造して例えばペレットとして使用する。この態様は本発明の樹脂洗浄剤を製品化する際に適している。
（２）以下に説明するポリエステル樹脂の溶融成形方法として、本発明の樹脂洗浄剤を使用する現場で製造してそのまま使用する。 The resin detergent of the present invention is used in the following various modes.
(1) A melt-mixed product of a compound capable of reacting with a terminal carboxyl group of a polyester resin to form an ester bond and a polyester resin is produced in advance and used as, for example, pellets. This embodiment is suitable for commercializing the resin detergent of the present invention.
(2) As a method for melt-molding a polyester resin described below, the polyester resin is manufactured on site using the resin detergent of the present invention and used as it is.
＜ポリエステル樹脂の溶融成形方法＞
　すなわち、本発明のポリエステル樹脂の溶融成形方法は、同一の成型機を使用し条件を変更して切替運転を行うに際し、切替運転に先立ち、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物を成型機に投入して内部に残存するポリエステル樹脂との溶融混合処理物から成る樹脂洗浄剤を生成させて成型機から排出させることを特徴とするポリエステル樹脂の溶融成形方法である。 <Polyester resin melt molding method>
That is, the polyester resin melt molding method of the present invention forms an ester bond by reacting with the terminal carboxyl group of the polyester resin prior to the switching operation when changing the conditions using the same molding machine. This is a polyester resin melt-molding method characterized in that a compound cleaning agent made of a melt-mixed product with a polyester resin remaining inside is injected into a molding machine and discharged from the molding machine.
　ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物は、成型機に投入して内部に残存するポリエステル樹脂に対する割合として、通常１～３０重量％、好ましくは５～２０重量％である。残存するポリエステル樹脂の量は成型機内の滞留量として容易に測定することが出来る。 The compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the polyester resin remaining in the molding machine. is there. The amount of the remaining polyester resin can be easily measured as the retention amount in the molding machine.
　また、上記の成形機としては、押出成型機、射出成形機などが挙げられる。条件を変更する態様としては、樹脂着色剤や他の添加剤を変更する場合が代表的であるが、固有粘度の異なるポリエステル樹脂に変更する場合などもある。 Moreover, examples of the molding machine include an extrusion molding machine and an injection molding machine. As a mode of changing the conditions, a case where the resin colorant and other additives are changed is representative, but there is also a case where the conditions are changed to a polyester resin having a different intrinsic viscosity.
　以下、本発明を実施例より更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail than the examples, but the present invention is not limited to the following examples unless it exceeds the gist.
　製造例１：
　ポリエステル樹脂（三菱化学製商品「ＮＯＶＡＰＥＸ」Ｇ２グレード（固有粘度：０．５９ｄＬ／ｇ）１００重量部にビスクレゾールフルオレン（ＢＣＦ）（ＪＦＥケミカル社製）１０重量部を加え、混合機で予備混合した後、以下に記載の要領で押出機で混練し、射出成形し、ペレット形状の樹脂洗浄剤（Ａ）を得た。ペレットの大きさは、直径３ｍｍ、長さ３ｍｍであった。なお、比較用にＢＣＦを含有しないポリエステル樹脂ペレットも製造した。 Production Example 1:
10 parts by weight of biscresol fluorene (BCF) (manufactured by JFE Chemical) was added to 100 parts by weight of a polyester resin (Mitsubishi Chemical product “NOVAPEX” G2 grade (intrinsic viscosity: 0.59 dL / g) and premixed with a mixer. Thereafter, the mixture was kneaded with an extruder and injection molded in the manner described below to obtain a pellet-shaped resin cleaning agent (A) having a diameter of 3 mm and a length of 3 mm. Polyester resin pellets containing no BCF were also produced.
（押出条件)
押出機；（株）池貝社製「ＰＣＭ４５」（スクリュー径４６ｍｍ）
射出条件；スクリュー回転数１８４ｒｐｍ
温度条件；３００℃
（射出成形条件)
射出成型機；（株）名機製作所製「Ｍ－１００Ｃ」
射出条件；スクリュー回転数８０ｒｐｍ、射出速度５０％、射出圧１０ＭＰＡ、背圧０ＭＰＡ
温度条件；２９０℃ (Extrusion conditions)
Extruder: “PCM45” (screw diameter 46 mm) manufactured by Ikegai Co., Ltd.
Injection conditions: Screw rotation speed 184rpm
Temperature condition: 300 ° C
(Injection molding conditions)
Injection molding machine; “M-100C” manufactured by Meiki Seisakusho Co., Ltd.
Injection conditions: Screw rotation speed 80rpm, injection speed 50%, injection pressure 10MPA, back pressure 0MPA
Temperature condition: 290 ° C
　製造例２：
　製造例１において、ビスクレゾールフルオレン（ＢＣＦ）の代わりに、オキサゾリン基含有ポリマー（日本触媒社製の「エポクロスＲＰＳ－１００５」）１０重量部を使用した以外は、製造例１と同様にして、ペレット形状の樹脂洗浄剤（Ｂ）を得た。 Production Example 2:
A pellet was produced in the same manner as in Production Example 1 except that 10 parts by weight of an oxazoline group-containing polymer (“Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.) was used instead of biscresol fluorene (BCF) in Production Example 1. A shaped resin cleaner (B) was obtained.
　製造例３：
　製造例１において、ビスクレゾールフルオレン（ＢＣＦ）の代わりに、エポキシ基含有ポリマー（日油製の「モディパーＡ４４００」）１０重量部を使用した以外は、製造例１と同様にして、ペレット形状の樹脂洗浄剤（Ｃ）を得た。 Production Example 3:
A pellet-shaped resin was produced in the same manner as in Production Example 1 except that 10 parts by weight of an epoxy group-containing polymer (“Modiper A4400” manufactured by NOF) was used instead of biscresol fluorene (BCF) in Production Example 1. A cleaning agent (C) was obtained.
　製造例４：
　製造例１において、ビスクレゾールフルオレン（ＢＣＦ）の代わりに、無水物基含有ポリマー（三菱化学社製の「ダイヤカナル３０」）１重量部を使用した以外は、製造例１と同様にして、ペレット形状の樹脂洗浄剤（Ｄ）を得た。 Production Example 4:
In Production Example 1, pellets were prepared in the same manner as in Production Example 1 except that 1 part by weight of an anhydride group-containing polymer ("Diacanal 30" manufactured by Mitsubishi Chemical Corporation) was used instead of biscresol fluorene (BCF). A resin cleaning agent (D) having a shape was obtained.
　実施例１（樹脂洗浄剤の評価）：
　前記と同じ条件を採用した着色ポリエステル樹脂ペレットの製造工程における押出機と射出成型機の洗浄を行った。着色ポリエステル樹脂ペレットの製造においては、前記と同一のポリエステル樹脂と、これに対して１０重量％の樹脂用着色剤（日本ピグメント社製のポリエステル用マスターバッチターコイズブルー）とを使用した。 Example 1 (Evaluation of resin cleaner):
The extruder and the injection molding machine were washed in the manufacturing process of colored polyester resin pellets employing the same conditions as described above. In the production of the colored polyester resin pellets, the same polyester resin as described above and 10% by weight of a resin colorant (polyester masterbatch turquoise blue manufactured by Nippon Pigment) were used.
　着色ポリエステル樹脂ペレットの製造後、押出機への供給を樹脂洗浄剤ペレット（Ａ）に切り換え、無色のポリエステル樹脂ペレットが得られるまで連続供給し、洗浄に必要な供給量を求めた（実施例１）。比較のため、上記と同様に、着色ポリエステル樹脂ペレットの製造後、押出機への供給をＢＣＦを含有しないポリエステル樹脂ペレットに切り換え、無色のポリエステル樹脂ペレットが得られるまで連続供給し、洗浄に必要な供給量を求めた（比較例１）。比較例１の場合の洗浄に必要な供給量は、実施例１に対して約２倍量であった。 After the production of the colored polyester resin pellets, the supply to the extruder was switched to the resin detergent pellets (A), and continuous supply was performed until colorless polyester resin pellets were obtained, and the supply amount necessary for cleaning was determined (Example 1). ). For comparison, in the same manner as above, after the production of colored polyester resin pellets, the supply to the extruder is switched to polyester resin pellets containing no BCF, and it is continuously supplied until colorless polyester resin pellets are obtained, which is necessary for washing. The supply amount was determined (Comparative Example 1). The supply amount necessary for cleaning in the case of Comparative Example 1 was about twice that of Example 1.
　実施例２～４：
　実施例１において、樹脂洗浄剤ペレット（Ａ）の代わりに、樹脂洗浄剤ペレット（Ｂ）～（Ｄ）を準じに使用し、実施例１と同様にして樹脂洗浄剤の評価を行った結果、実施例１と同様の結果を得た。すなわち、実施例２～４の場合も、比較例１の場合の洗浄に必要な供給量は実施例２～４に対して約２倍量であった。 Examples 2-4:
In Example 1, instead of the resin detergent pellet (A), the resin detergent pellets (B) to (D) were used according to the evaluation results of the resin detergent in the same manner as in Example 1. The same results as in Example 1 were obtained. That is, in Examples 2 to 4, the supply amount necessary for cleaning in Comparative Example 1 was about twice that in Examples 2 to 4.

Claims (3)

  1. 　原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用する樹脂洗浄剤であって、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物とポリエステル樹脂との溶融混合処理物から成ることを特徴とする樹脂洗浄剤。 A resin cleaning agent used for cleaning the inside of molding processing equipment using a polyester resin as a raw material resin, and a melt-mixed processed product of a polyester resin and a compound that can react with a terminal carboxyl group of the polyester resin to form an ester bond A resin cleaning agent comprising:
  2. 　ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物が、以下に記載の一般式（１）で表されるフルオレン骨格を有する化合物（Ａ）、分子内に２個以上のオキサゾリン基を有する化合物（Ｂ）、分子内に２個以上のエポキシ基を有する化合物（Ｃ）、酸無水物基を有する化合物（Ｄ）の群から選択される少なくとも１種の化合物である請求項１に記載の樹脂洗浄剤。
    Figure JPOXMLDOC01-appb-C000001
      
    （化学式（１）中のＡは、水素原子または－（ＣＨ２）ｎ－Ｈ基であり、ここでｎは１以上の整数を表す。）     The compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond is a compound (A) having a fluorene skeleton represented by the following general formula (1), two or more oxazoline groups in the molecule The compound (B) having at least one compound selected from the group consisting of a compound (C) having two or more epoxy groups in the molecule and a compound (D) having an acid anhydride group. The resin cleaning agent as described.
    Figure JPOXMLDOC01-appb-C000001
    (A in the chemical formula (1) is a hydrogen atom or a — (CH 2 ) n —H group, where n represents an integer of 1 or more.)
  3. 　ポリエステル樹脂の溶融成形方法において、同一の成型機を使用し条件を変更して切替運転を行うに際し、切替運転に先立ち、ポリエステル樹脂の末端カルボキシル基と反応してエステル結合を形成し得る化合物を成型機に投入して内部に残存するポリエステル樹脂との溶融混合処理物から成る樹脂洗浄剤を生成させて成型機から排出させることを特徴とするポリエステル樹脂の溶融成形方法。 In the polyester resin melt molding method, when using the same molding machine to change the conditions and performing the switching operation, prior to the switching operation, molding a compound that can react with the terminal carboxyl group of the polyester resin to form an ester bond A method for melt-molding a polyester resin, characterized in that a resin cleaning agent comprising a melt-mixed product with a polyester resin remaining in the machine is generated and discharged from a molding machine.
PCT/JP2018/002226 2017-02-14 2018-01-25 Resin cleaning agent and method for melt molding polyester resin WO2018150837A1 (en)

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JPH0827335A (en) * 1994-07-15 1996-01-30 Idemitsu Petrochem Co Ltd Cleaning agent for resin in molding machine
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WO2008146822A1 (en) * 2007-05-29 2008-12-04 Asahi Kasei Chemicals Corporation Purging agent and process for purging a resin molding machine with the same

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