CN110268016B - Resin cleaning agent and method for melt molding polyester resin - Google Patents
Resin cleaning agent and method for melt molding polyester resin Download PDFInfo
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- CN110268016B CN110268016B CN201880010871.8A CN201880010871A CN110268016B CN 110268016 B CN110268016 B CN 110268016B CN 201880010871 A CN201880010871 A CN 201880010871A CN 110268016 B CN110268016 B CN 110268016B
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
- B29C33/72—Cleaning
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- 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
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- 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
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- 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
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Detergent Compositions (AREA)
Abstract
The invention provides a novel resin cleaning agent for cleaning the interior of molding processing equipment using polyester resin as raw material resin. The resin cleaning agent is used for cleaning the inside of a molding processing device using a polyester resin as a raw material resin, and comprises a melt-mixed treatment product of a compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond and the polyester resin.
Description
Technical Field
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 for cleaning the inside of molding equipment such as an extruder and an injection molding equipment.
Background
In the field of molding of thermoplastic resins, for example, when switching the raw material resin material and switching the color, the inside of the molding equipment is cleaned. This enables, for example, the discharge of the residue of the material used before, when the material is switched. In addition, the inside of the molding equipment is also cleaned in order to remove carbide and ensure product quality.
Conventionally, as a resin cleaning agent as described above, the following thermoplastic resin composition is known (patent document 1).
"a thermoplastic resin composition for cleaning, which comprises, per 100 parts by mass of (A) a polypropylene:
(B) 0 to 50 parts by mass of a thermoplastic resin incompatible with the component (A);
(C) 0.5 to 50 parts by mass of a thermoplastic resin for compatibilizing the component (A) and the component (B); and
(D) 0.5 to 15 parts by mass of a surfactant mixture containing 1 or more kinds selected from anionic surfactants and 1 or more kinds selected from nonionic surfactants. "
The above-mentioned thermoplastic resin composition for washing improves the disadvantages of most of the proposed thermoplastic resin compositions for washing, and has an advantage that it is easy to replace polypropylene when continuing to mold polypropylene after washing.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012-140481
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a novel resin cleaning agent for cleaning the interior of a molding processing device using polyester resin as raw material resin.
Technical solution for solving technical problem
The present inventors have made intensive studies to achieve the above object, and as a result, have obtained a finding that the above object can be achieved by skillfully utilizing a specific compound.
That is, the present invention is a resin cleaning agent characterized in that: the resin cleaning agent is used for cleaning the inside of a molding processing device using a polyester resin as a raw material resin, and comprises a melt-mixed treatment product of a compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond and the polyester resin.
Another aspect of the present invention is a method for melt-molding a polyester resin, comprising: in a method for melt-molding a polyester resin, when a switching operation is performed by changing conditions using the same molding machine, a compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond is fed into the molding machine before the switching operation, and a resin cleaning agent containing a melt-mixed product of the compound and the polyester resin remaining inside is produced and discharged from the molding machine.
In a preferred embodiment of the present invention, at least 1 compound selected from the group consisting of the compound (a) having a fluorene skeleton represented by the following general formula (1), the compound (B) having 2 or more oxazoline groups in a molecule, the compound (C) having 2 or more epoxy groups in a molecule, and the compound (D) having an acid anhydride group is used as the compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond.
Effects of the invention
The above object can be achieved by the present invention.
Detailed Description
The present invention will be described in detail below.
< resin cleaning agent >
First, the compound (a) having a fluorene skeleton represented by the above general formula (1) will be described.
In the general formula (1), the compound represented by a hydrogen atom is bisphenol fluorene (BPFL), and the compound represented by a methyl group is Biscresolfluorene (BCF). These compounds are well known as optical functional materials. In the present invention, 2 hydroxyl groups are important in the above-mentioned compounds, and a in the chemical formula (1) may be an alkyl group having an arbitrary carbon number, for example, a lower alkyl group having 6 or less carbon atoms, or a polyethylene chain, in addition to a hydrogen atom and a methyl group. These may have a straight chain structure or a branched structure. The compounds that can be readily obtained are BPFL or BCF. The polyethylene chain can be obtained, for example, by methyl polyaddition of polyethylene with BCF. Therefore, the compound having a fluorene skeleton represented by the general formula (1) has excellent heat resistance due to the skeleton.
Next, the compound (B) having 2 or more oxazoline groups in a molecule will be described.
The compound having 2 or more oxazoline groups in the molecule is not particularly limited, and examples thereof include 2 '-methylenebis (2-oxazoline), 2' -ethylenebis (4-methyl-2-oxazoline), 2 '-propylenebis (2-oxazoline), 2' -tetramethylenebis (2-oxazoline), 2 '-hexamethylenebis (2-oxazoline), 2' -octamethylenebis (2-oxazoline), 2 '-p-phenylenebis (4, 4' -dimethyl-2-oxazoline), 2 '-p-phenylenebis (4-methyl-2-oxazoline), and 2, 2' -p-phenylenebis (4-phenyl-2-oxazoline).
In addition to the above compounds, oxazoline group-containing polymers may 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, or 2-isopropenyl-2-oxazoline. If necessary, other monomers may be copolymerized. The polymerization method of the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be used.
As commercially available oxazoline group-containing polymers, there are exemplified EPOCROS series manufactured by Japanese catalyst Co., Ltd., specifically water-soluble type "WS-500", "WS-700", solid type "RPS-1005", and the like.
Next, the compound (C) having 2 or more epoxy groups in the molecule will be described.
The compound having 2 or more epoxy groups in the molecule is not particularly limited, and various compounds other than the glycidyl ether type epoxy compound and the alicyclic epoxy compound can be used.
Examples of the glycidyl ether type epoxy compound include diglycidyl ethers or polyglycidyl ethers of polyhydric phenols having an aromatic core or alkylene oxide adducts thereof, and diglycidyl ethers or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Specific examples thereof include: diglycidyl ethers or polyglycidyl ethers of bisphenol a, bisphenol F, bisphenol S, hydrogenated bisphenol a, hydrogenated bisphenol F, hydrogenated bisphenol S, bisphenol fluorene, and alkylene oxide adduct of these phenols; diglycidyl ethers of alkylene glycols such as ethylene glycol, 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; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol, or alkylene oxide adducts of these diols; diglycidyl ethers or triglycidyl ethers of trimethylolethane, trimethylolpropane and glycerol or of alkylene oxide adducts of these trihydric alcohols; polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether, triglycidyl ether, and tetraglycidyl ether of pentaerythritol, or alkylene oxide adducts thereof; a novolac type epoxy resin; a cresol novolac resin; and compounds obtained by substituting an aromatic nucleus of these compounds with a halogen.
Examples of the alicyclic epoxy compound include compounds containing cyclohexene oxide or cyclopentene oxide, which are obtained by epoxidizing a compound having a cycloalkane ring such as cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or a peracid. Specific examples thereof include 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexane-methyl-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylcyclohexane oxide, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ', 4' -epoxy-6 '-methylcyclohexaneformate, methylenebis (3, 4-epoxycyclohexane), dicyclopentadiene diepoxide, bis (3, 4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxycyclohexanecarboxylate), epoxidized tetrabenzyl alcohol, lactone-modified 3, 4-epoxycyclohexylmethyl-3', 4' -epoxycyclohexanecarboxylate, lactone-modified epoxidized tetrahydrobenzyl alcohol, cyclohexene oxide, and the like.
Many compounds having 2 or more epoxy groups in the molecule are commercially available and can be easily obtained. Examples of commercially available products of bisphenol A epichlorohydrin type epoxy resins and sorbitol polyglycidyl ethers include, for example, those sold under the trade names "Denacol EX-611", "Denacol EX-612", "Denacol EX-614B" and "Denacol EX-622" manufactured by Nagasescelmex; commercially available products of polyglycerol polyglycidyl ether include those available under the trade names "Denacol EX-512" and "Denacol EX-521" from Nagasechemtex; commercially available products of pentaerythritol polyglycidyl ether include, for example, those available under the trade name "Denacol EX-411" from Nagaseschemtex; examples of commercially available products of the diglycerol polyglycidyl ether include, for example, those sold under the trade name "Denacol EX-421" manufactured by Nagaseschemtex; commercially available products of glycerol polyglycidyl ether include, for example, those available under the trade names "Denacol EX-313" and "Denacol EX-314" from Nagaseschemtex; examples of commercially available products of trimethylolpropane polyglycidyl ether include "Denacol EX-321" manufactured by Nagaseschemtex corporation; commercially available products of neopentyl glycol diglycidyl ether include, for example, those sold under the trade name "Denacol EX-211" manufactured by Nagaseschemtex corporation; commercially available products of 1, 6-hexanediol diglycidyl ether include, for example, those sold under the trade name "Denacol EX-212" manufactured by Nagaseschemtex; commercially available ethylene glycol diglycidyl ether products include, for example, those sold under the trade names "Denacol EX-810" and "Denacol EX-811" manufactured by Nagaseschemtex; examples of commercially available diethylene glycol diglycidyl ether include those sold under the trade names "Denacol EX-850" and "Denacol EX-851" manufactured by Nagaseschemtex; examples of commercially available products of polyethylene glycol diglycidyl ether include those manufactured by Nagasechemtex under the trade names "Denacol EX-821", "Denacol EX-830", "Denacol EX-832", "Denacol EX-841" and "Denacol EX-861"; commercially available products of propylene glycol diglycidyl ether include, for example, those sold under the trade name "Denacol EX-911" manufactured by Nagasechemtex corporation; commercially available products of polypropylene glycol diglycidyl ether include, for example, diglycidyl aniline, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N ' -diglycidylaminomethyl) cyclohexane, and the like, which are available under the trade names "Denacol EX-941", "Denacol EX-920" and "Denacol EX-931" from Nagasechemtex corporation.
Commercial products of epoxy-containing polymers may also be used. Examples of commercially available epoxy group-containing polymers having glycidyl groups formed by bonding epoxy groups to the main chain of a graft copolymer having a polyolefin as the main chain and a vinyl polymer as the side chain include "MODIPER A4100", "MODIPERA 4300" and "MODIPERA 4400" manufactured by Nikkiso Co.
Next, the compound (D) having an acid anhydride group will be described.
The compound having an acid anhydride group is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, and phthalic anhydride. Examples of the compound (polybasic acid anhydride) having 2 or more acid anhydride groups in the molecule include aliphatic or aromatic tetrabasic acid dianhydrides such as biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, and diphenyl sulfone tetracarboxylic acid dianhydride.
In addition to the above compounds, polymers having an acid anhydride group may also be used. The polymer having an acid anhydride group can be obtained by (co) polymerizing maleic anhydride.
Commercial products of the polymers containing anhydride groups may also be used. For example, commercially available products of copolymers of α -olefins and maleic anhydride include trade names "dicarana", "MODIC F532", and "MODIC F534A" manufactured by mitsubishi chemical corporation. Maleic anhydride-modified polyolefins obtained by graft copolymerization of maleic anhydride are known. For example, there are products "UMEX 2000" manufactured by sanyo chemical industry corporation.
The resin cleaning agent of the present invention comprises a melt-mixed product of a polyester resin and a compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond. The polyester resin used as the base material of the resin cleaning agent is a general-purpose polyester resin, and for example, when the inside of the molding machine is cleaned when the raw material resin material is switched, the polyester resin to be used subsequently after the cleaning is usually selected.
The polyester resin may be a homopolyester or a copolyester. In the case of a homopolyester, a polyester resin obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol is preferable. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2, 6-naphthalenedicarboxylic acid, and examples of the aliphatic diol include ethylene glycol, diethylene glycol, and 1, 4-cyclohexanedimethanol. As a representative polyester, polyethylene terephthalate and the like can be exemplified. On the other hand, in the case of a copolyester, as the dicarboxylic acid component, there may be mentioned one or two or more of isophthalic acid, phthalic acid, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, hydroxycarboxylic acids (e.g., p-hydroxybenzoic acid, etc.); examples of the diol component include one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol, and the like.
The compound capable of forming an ester bond by reacting with the terminal carboxyl group of the polyester resin is not limited to the above-mentioned compounds, and other examples include isocyanate compounds and carbodiimide compounds. These compounds are also known as cross-linking agents.
The amount of the compound capable of reacting 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 base polyester resin.
In the present invention, additives described in the above 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 be blended. The amount of these additives may be appropriately selected, and the proportion of these additives to the base polyester resin is usually 1 to 30% by weight, preferably 5 to 20% by weight.
The resin cleaning agent of the present invention is generally produced as follows. That is, the above components are premixed by a mixer such as a henschel mixer, a tumbler mixer, or a kneader, and then melt-mixed. The melt mixing treatment can be performed using an extruder, a heated roll, or a banbury mixer. Generally, the pellets are molded by melt mixing treatment using an extruder. The size thereof may be appropriately selected in consideration of the size of the feeding zone of the extruder, injection molding equipment, and the like. The conditions for the melt-mixing treatment in the extruder may be known conditions for producing polyester resin pellets.
The resin cleaning agent of the present invention is used for cleaning the inside of a molding machine using a polyester resin as a raw material resin, and further, since the polyester resin is used as a base material, there is a great advantage that a resin different from the polyester resin is not mixed in the molding machine, that is, there is no contamination of the resin accompanying the cleaning of the inside of the molding machine at all.
The compatibilizer used in the invention described in patent document 1 is an additive used when polymers are phase-separated from each other and cannot be uniformly mixed in the production of a resin (polymer alloy) in which 2 kinds of polymer materials are mixed, and is an additive for forming a copolymer of the 2 kinds of polymers.
Therefore, the action and effect of each of the above-mentioned compounds used in the resin cleaning agent of the present invention are different from those of conventional compatibilizing agents, and are presumed as follows.
In the production of the resin cleaning agent 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 acid anhydride group of the compound (D) reacts with the terminal carboxyl group (-COOH) of the base PET (a) by melt-mixing treatment to form an ester bond. However, the relative viscosity decreases due to the formation of a branched structure. Of course, since a small amount of water is generated by dehydration reaction due to heat during melt mixing treatment, and an ester bond is hydrolyzed, all the reactive groups of the above-mentioned compounds do not disappear.
In the production of the resin cleaning agent of the present invention, the resin cleaning agent is melt-mixed with the polyester resin adhering to and remaining in the molding processing equipment and moved by the same melt-mixing treatment as described above. The flow inside the molding equipment of the resin cleaning agent of the present invention is lower in viscosity than that of the base material PET (a) alone, and is excellent and exhibits a high cleaning effect. However, the reactive group of each of the above compounds reacts with a terminal carboxyl group (-COOH) of PET (b) attached to and remaining inside the molding processing device (crosslinking reaction) to form an ester bond. In this case, the branched structure is formed as described above, the relative viscosity is further reduced, and the resin composition can be easily discharged from the inside of the molding machine. The carboxyl group also includes a carboxyl group generated by a decomposition reaction in the molding equipment.
When the compound a having a fluorene skeleton represented by the general formula (1) is an alkyl group or a polyethylene chain, a resin cleaning agent having improved heat resistance can be obtained as follows. That is, in the production of the resin cleaning agent, polystyrene is used together with the base polyester resin, and the base polyester resin is copolymerized with polystyrene via a hydroxyl group and an alkyl group or a polyethylene chain, thereby improving the heat resistance of the base polyester resin. Specifically, polystyrene has the characteristics of not yellowing and not scorching to black at high temperatures, and therefore can compensate for these disadvantages of polyester resins that gel or yellow or scorch to black at high temperatures.
The resin cleaning agent of the present invention can be used in the following manner.
(1) A melt-mixed treatment product of a compound capable of reacting with a terminal carboxyl group of a polyester resin to form an ester bond and the polyester resin is prepared in advance and used, for example, in the form of pellets. This mode is suitable for use in the production of the resin cleaning agent of the present invention.
(2) The polyester resin melt molding method described below is produced on site using the resin cleaning agent of the present invention and used as it is.
< method for melt-molding polyester resin >
That is, the method for melt-molding a polyester resin of the present invention is characterized in that: when the switching operation is performed by changing the conditions using the same molding machine, a compound capable of reacting with the terminal carboxyl group of the polyester resin to form an ester bond is fed into the molding machine before the switching operation, and a resin cleaning agent containing a melt-mixed product of the compound and the polyester resin remaining inside is produced and discharged from the molding machine.
The proportion of the compound capable of reacting with the terminal carboxyl group of the polyester resin to form an ester bond to the polyester resin remaining inside the molding machine is usually 1 to 30% by weight, preferably 5 to 20% by weight. The retention in the molding machine can be easily measured as the amount of the residual polyester resin.
The molding machine may be an extrusion molding machine, an injection molding machine, or the like. As a typical method of changing the conditions, the resin colorant and other additives may be changed, but there is a case where the resin colorant and other additives are changed to polyester resins having different intrinsic viscosities.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the invention does not depart from the gist thereof.
Production example 1:
100 parts by weight of a polyester resin (product of Mitsubishi chemical "NOVAPEX" grade G2 (intrinsic viscosity: 0.59dL/G)) was premixed with 10 parts by weight of dicresol fluorene (BCF) (manufactured by JFE chemical Co., Ltd.) in a mixer, and then kneaded and injection-molded by an extruder in the following manner to obtain a pellet-shaped resin cleaning agent (A). The size of the pellets was 3mm in diameter and 3mm in length. For comparison, polyester resin pellets containing no BCF were also produced.
(extrusion Condition)
An extruder: "PCM 45" (screw diameter 46mm), manufactured by Kupffer corporation
Injection conditions were as follows: screw rotation speed 184rpm
Temperature conditions: 300 deg.C
(conditions of injection Molding)
An injection molding machine: "M-100C" manufactured by Kabushiki Kaisha "
Injection conditions were as follows: screw rotation speed 80rpm, injection speed 50%, injection pressure 10MPA, back pressure 0MPA
Temperature conditions: 290 deg.C
Production example 2:
a resin cleaning agent (B) in the form of pellets was obtained in the same manner as in production example 1 except that 10 parts by weight of an oxazoline group-containing polymer ("EPOCROS RPS-1005" manufactured by Nippon catalyst Co., Ltd.) was used in place of biscresol fluorene (BCF) in production example 1.
Production example 3:
a resin cleaning agent (C) in the form of pellets was obtained in the same manner as in production example 1 except that 10 parts by weight of an epoxy group-containing polymer ("MODIPERA 4400" manufactured by Nichisu oil) was used in production example 1 in place of biscresol fluorene (BCF).
Production example 4:
a resin cleaning agent (D) in the form of pellets was obtained in the same manner as in production example 1 except that 1 part by weight of an anhydride group-containing polymer ("DIACARNA 30", manufactured by Mitsubishi chemical corporation) was used in production example 1 in place of biscresol fluorene (BCF).
Example 1 (evaluation of resin cleaning agent):
the extruder and the injection molding machine in the production process of the colored polyester resin pellets under the same conditions as described above were cleaned. In the production of the colored polyester resin pellets, the same polyester resin as described above and 10 wt% of a colorant for resin (Master batch turquoise blue for polyester manufactured by nippment corporation, japan) were used.
After production of colored polyester resin pellets, supply to the extruder was switched to resin detergent pellets (a), and the resin detergent pellets were continuously supplied until colorless polyester resin pellets were obtained, and the supply amount necessary for cleaning was determined (example 1). For comparison, after producing colored polyester resin pellets, the supply to the extruder was switched to polyester resin pellets containing no BCF, and the supply was continued until colorless polyester resin pellets were obtained, and the supply amount necessary for washing was determined (comparative example 1). The supply amount required for cleaning in the case of comparative example 1 was about 2 times the amount of that in example 1.
Examples 2 to 4:
in example 1, resin detergent pellets (B) to (D) were prepared and used in place of the resin detergent pellet (a), and evaluation of the resin detergent was performed in the same manner as in example 1, and as a result, the same results as in example 1 were obtained. That is, examples 2 to 4 also include: the supply amount required for cleaning in the case of comparative example 1 was about 2 times the amount of the supply amount required in examples 2 to 4.
Claims (2)
1. A resin cleaning agent is characterized in that:
the resin cleaning agent is used for cleaning the inside of a molding processing device using a polyester resin as a raw material resin, and comprises a melt-mixed processed product of a compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond and the polyester resin,
the compound capable of reacting with the terminal carboxyl group of the polyester resin to form an ester bond is at least 1 compound selected from the group consisting of a compound (A) having a fluorene skeleton represented by the following general formula (1), a compound (B) having 2 or more oxazoline groups in the molecule, a compound (C) having 2 or more epoxy groups in the molecule, and a compound (D) having an acid anhydride group,
a in the chemical formula (1) is a hydrogen atom or- (CH)2)n-H group, wherein n represents an integer of 1 or more.
2. A method for melt-molding a polyester resin, characterized by comprising:
in a method for melt-molding a polyester resin, when a switching operation is performed by changing conditions using the same molding machine, a compound capable of reacting with a terminal carboxyl group of the polyester resin to form an ester bond is fed into the molding machine before the switching operation, and a resin cleaning agent containing a melt-mixed product of the compound and the polyester resin remaining inside is produced and discharged from the molding machine,
the compound capable of reacting with the terminal carboxyl group of the polyester resin to form an ester bond is at least 1 compound selected from the group consisting of a compound (A) having a fluorene skeleton represented by the following general formula (1), a compound (B) having 2 or more oxazoline groups in the molecule, a compound (C) having 2 or more epoxy groups in the molecule, and a compound (D) having an acid anhydride group,
a in the chemical formula (1) is a hydrogen atom or- (CH)2)n-H group, wherein n represents an integer of 1 or more.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-024816 | 2017-02-14 | ||
| JP2017024816A JP6326157B1 (en) | 2017-02-14 | 2017-02-14 | Resin cleaner |
| JP2017-024817 | 2017-02-14 | ||
| JP2017024817A JP6326158B1 (en) | 2017-02-14 | 2017-02-14 | Resin cleaner |
| JP2017-044051 | 2017-03-08 | ||
| JP2017044050A JP6326162B1 (en) | 2017-03-08 | 2017-03-08 | Resin cleaner |
| JP2017-044050 | 2017-03-08 | ||
| JP2017044051A JP6326163B1 (en) | 2017-03-08 | 2017-03-08 | Resin cleaner |
| PCT/JP2018/002226 WO2018150837A1 (en) | 2017-02-14 | 2018-01-25 | Resin cleaning agent and method for melt molding polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110268016A CN110268016A (en) | 2019-09-20 |
| CN110268016B true CN110268016B (en) | 2022-05-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880010871.8A Active CN110268016B (en) | 2017-02-14 | 2018-01-25 | Resin cleaning agent and method for melt molding polyester resin |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20190111982A (en) |
| CN (1) | CN110268016B (en) |
| TW (1) | TW201840704A (en) |
| WO (1) | WO2018150837A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110802089B (en) * | 2019-10-17 | 2021-10-26 | 一汽奔腾轿车有限公司 | Cleaning method for water-based paint conveying and mixing system after line building |
| CN115305157A (en) * | 2022-09-23 | 2022-11-08 | 广东粤港澳大湾区黄埔材料研究院 | Epoxy resin cleaning agent and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239099A (en) * | 1991-01-09 | 1992-08-26 | Chisso Corp | Washing composition and washing method |
| JPH0827335A (en) * | 1994-07-15 | 1996-01-30 | Idemitsu Petrochem Co Ltd | Cleaning agent for resin in molding machine |
| JP2005200443A (en) * | 2004-01-13 | 2005-07-28 | Is:Kk | Method of cleaning inorganic member |
| CN101679925A (en) * | 2007-05-29 | 2010-03-24 | 旭化成化学株式会社 | Purging agent and process for purging a resin molding machine with the same |
| CN101812385A (en) * | 2009-02-24 | 2010-08-25 | 住友化学株式会社 | Cleaning compositions and use it to come the method for cleaning liquor crystalline polyester production device |
| CN102574995A (en) * | 2009-10-14 | 2012-07-11 | 株式会社自动网络技术研究所 | Modified recycled polyester resin and molded article using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5755444B2 (en) | 2010-12-28 | 2015-07-29 | ダイセルポリマー株式会社 | Thermoplastic resin composition for cleaning |
-
2018
- 2018-01-25 CN CN201880010871.8A patent/CN110268016B/en active Active
- 2018-01-25 WO PCT/JP2018/002226 patent/WO2018150837A1/en active Application Filing
- 2018-01-25 KR KR1020197023049A patent/KR20190111982A/en unknown
- 2018-02-08 TW TW107104470A patent/TW201840704A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239099A (en) * | 1991-01-09 | 1992-08-26 | Chisso Corp | Washing composition and washing method |
| JPH0827335A (en) * | 1994-07-15 | 1996-01-30 | Idemitsu Petrochem Co Ltd | Cleaning agent for resin in molding machine |
| JP2005200443A (en) * | 2004-01-13 | 2005-07-28 | Is:Kk | Method of cleaning inorganic member |
| CN101679925A (en) * | 2007-05-29 | 2010-03-24 | 旭化成化学株式会社 | Purging agent and process for purging a resin molding machine with the same |
| CN101812385A (en) * | 2009-02-24 | 2010-08-25 | 住友化学株式会社 | Cleaning compositions and use it to come the method for cleaning liquor crystalline polyester production device |
| CN102574995A (en) * | 2009-10-14 | 2012-07-11 | 株式会社自动网络技术研究所 | Modified recycled polyester resin and molded article using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110268016A (en) | 2019-09-20 |
| WO2018150837A1 (en) | 2018-08-23 |
| TW201840704A (en) | 2018-11-16 |
| KR20190111982A (en) | 2019-10-02 |
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