WO2022202672A1 - ポリエステル樹脂とその製造方法及び塗料 - Google Patents
ポリエステル樹脂とその製造方法及び塗料 Download PDFInfo
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- WO2022202672A1 WO2022202672A1 PCT/JP2022/012654 JP2022012654W WO2022202672A1 WO 2022202672 A1 WO2022202672 A1 WO 2022202672A1 JP 2022012654 W JP2022012654 W JP 2022012654W WO 2022202672 A1 WO2022202672 A1 WO 2022202672A1
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- Prior art keywords
- derived
- polyester resin
- biomass
- acid
- carbon atoms
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- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- JNDJSWFQRHPRLQ-UHFFFAOYSA-J anthracene-1,2-dicarboxylate;titanium(4+) Chemical compound [Ti+4].C1=CC=CC2=CC3=C(C([O-])=O)C(C(=O)[O-])=CC=C3C=C21.C1=CC=CC2=CC3=C(C([O-])=O)C(C(=O)[O-])=CC=C3C=C21 JNDJSWFQRHPRLQ-UHFFFAOYSA-J 0.000 description 1
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- OUOCBXDNCIRWDY-UHFFFAOYSA-J butanedioate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O OUOCBXDNCIRWDY-UHFFFAOYSA-J 0.000 description 1
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- KXACYFLWZJVZST-UHFFFAOYSA-J decanedioate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)CCCCCCCCC([O-])=O.[O-]C(=O)CCCCCCCCC([O-])=O KXACYFLWZJVZST-UHFFFAOYSA-J 0.000 description 1
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- GOPWOUQJIMLDDM-UHFFFAOYSA-N dibutyl benzene-1,3-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC(C(=O)OCCCC)=C1 GOPWOUQJIMLDDM-UHFFFAOYSA-N 0.000 description 1
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- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- ZBIWVPJOSBFUON-UHFFFAOYSA-J naphthalene-1,2,3,7-tetracarboxylate;titanium(4+) Chemical compound [Ti+4].C1=C(C([O-])=O)C(C([O-])=O)=C(C([O-])=O)C2=CC(C(=O)[O-])=CC=C21 ZBIWVPJOSBFUON-UHFFFAOYSA-J 0.000 description 1
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- LATKICLYWYUXCN-UHFFFAOYSA-N naphthalene-1,3,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 LATKICLYWYUXCN-UHFFFAOYSA-N 0.000 description 1
- WJLZQPZUSAVHLF-UHFFFAOYSA-B naphthalene-1,3,7-tricarboxylate titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)c1ccc2cc(cc(C([O-])=O)c2c1)C([O-])=O.[O-]C(=O)c1ccc2cc(cc(C([O-])=O)c2c1)C([O-])=O.[O-]C(=O)c1ccc2cc(cc(C([O-])=O)c2c1)C([O-])=O.[O-]C(=O)c1ccc2cc(cc(C([O-])=O)c2c1)C([O-])=O WJLZQPZUSAVHLF-UHFFFAOYSA-B 0.000 description 1
- XOXQQKPLCPYWIC-UHFFFAOYSA-J naphthalene-1,3-dicarboxylate;titanium(4+) Chemical compound [Ti+4].C1=CC=CC2=CC(C(=O)[O-])=CC(C([O-])=O)=C21.C1=CC=CC2=CC(C(=O)[O-])=CC(C([O-])=O)=C21 XOXQQKPLCPYWIC-UHFFFAOYSA-J 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- CFHYYGHJMPIOHE-UHFFFAOYSA-J octane-1,1,1,2-tetracarboxylate;titanium(4+) Chemical compound [Ti+4].CCCCCCC(C([O-])=O)C(C([O-])=O)(C([O-])=O)C([O-])=O CFHYYGHJMPIOHE-UHFFFAOYSA-J 0.000 description 1
- WDAISVDZHKFVQP-UHFFFAOYSA-N octane-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)CCCCC(C(O)=O)CC(O)=O WDAISVDZHKFVQP-UHFFFAOYSA-N 0.000 description 1
- HLQKKXPTQUDRCG-UHFFFAOYSA-J octanoate titanium(4+) Chemical compound [Ti+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HLQKKXPTQUDRCG-UHFFFAOYSA-J 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VLQDLYQOMLDQOW-UHFFFAOYSA-N pentan-1-ol;titanium Chemical compound [Ti].CCCCCO.CCCCCO.CCCCCO.CCCCCO VLQDLYQOMLDQOW-UHFFFAOYSA-N 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GFNGXEPRHYGJQP-UHFFFAOYSA-J phthalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C1=CC=CC=C1C([O-])=O.[O-]C(=O)C1=CC=CC=C1C([O-])=O GFNGXEPRHYGJQP-UHFFFAOYSA-J 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- OJTDGPLHRSZIAV-UHFFFAOYSA-N propane-1,2-diol Chemical compound CC(O)CO.CC(O)CO OJTDGPLHRSZIAV-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- CXJNRRJXWSODHK-UHFFFAOYSA-J terephthalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1.[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 CXJNRRJXWSODHK-UHFFFAOYSA-J 0.000 description 1
- MMLHSHZVZZRNRY-UHFFFAOYSA-J titanium(4+) tetraformate Chemical compound [Ti+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O MMLHSHZVZZRNRY-UHFFFAOYSA-J 0.000 description 1
- WYKQDEPZMVTTSJ-UHFFFAOYSA-J titanium(4+);tetrabenzoate Chemical compound [Ti+4].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 WYKQDEPZMVTTSJ-UHFFFAOYSA-J 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
Definitions
- the present invention relates to a polyester resin, a method for producing the same, and a paint.
- This application claims priority to Japanese Patent Application No. 2021-047375 filed in Japan on March 22, 2021 and Japanese Patent Application No. 2021-154388 filed in Japan on September 22, 2021, the contents of which are hereby incorporated by reference. to refer to.
- polyester resins are widely used as raw materials for fibers, films, and the like, and also as binder resins for paints, inks, toners, and the like.
- binder resins for paints, inks, toners, and the like.
- Patent Document 1 proposes a toner using a polyester resin obtained by copolymerizing biomass-derived isosorbide, which is a toner having good fixability, hot offset resistance, and storage stability while reducing environmental load. is shown to be obtained.
- Patent Document 2 proposes a method for producing a polyester resin by introducing recycled PET into an apparatus together with other raw materials.
- Patent Document 3 discloses an attempt to reduce the coloration of polyester resin using isosorbide by devising a catalyst. Further, regarding the phenomenon of low solvent solubility, Patent Document 4 proposes a solvent-soluble polyester obtained by copolymerizing isosorbide.
- Patent Document 2 uses organotin and lead-containing materials as catalysts, which are feared to have an adverse effect on the human body and the environment. When no catalyst is used, the production time is lengthened, and it is not clear whether the resin can be obtained in the same short time when other catalysts that do not have the above concerns are used.
- the technique of Patent Document 2 does not refer to raw materials other than recycled polyethylene terephthalate, and there is room for further study from the viewpoint of reducing environmental impact.
- the present invention can be used for light-colored inks and paints while considering the environment and safety by reducing the amount of petroleum-derived raw materials used, has good solvent solubility, excellent storage stability, and has a light color.
- An object of the present invention is to provide a polyester resin, a method for producing the same, a paint, an ink, an adhesive, and an image-forming material.
- the present invention has the following aspects.
- a structural unit derived from at least one of a biomass-derived polyhydric alcohol and a biomass-derived polycarboxylic acid, and a structural unit derived from polyethylene terephthalate, wherein the polyethylene terephthalate relative to 100% of all carbon atoms A polyester resin having a derived carbon atom ratio of 5 to 40% and a methyl ethyl ketone insoluble content of 5% by mass or less.
- the polyester resin according to [1] wherein the structural unit derived from a biomass-derived polyhydric alcohol is a structural unit derived from a heterocyclic polyhydric alcohol.
- the ratio of carbon atoms derived from the biomass-derived polyhydric alcohol and the biomass-derived polycarboxylic acid is 1 to 95% with respect to the total carbon atoms contained in the polyester resin, [1] to [ 5], the polyester resin according to any one of the above items.
- the carbon atom ratio derived from the biomass-derived polyhydric alcohol, the biomass-derived polycarboxylic acid and the polyethylene terephthalate is 6 to 100% with respect to the total carbon atoms contained in the polyester resin, [ 1] The polyester resin according to any one of [6].
- the polyester resin having a particle size of 1 to 2 mm is fractionated by sieving, and the L value is 40 or more and the a value is 2.4 or less when measured with a spectrophotometer.
- the polyester resin according to any one of [8]. [9] A paint containing the polyester resin according to any one of [1] to [8] and a solvent. [10] An ink containing the polyester resin according to any one of [1] to [8]. [11] An adhesive material containing the polyester resin according to any one of [1] to [8]. [12] An image forming material comprising the polyester resin of any one of [1] to [8].
- At least one of an esterification reaction and a transesterification reaction in which a raw material containing at least one of a biomass-derived polyhydric alcohol and a biomass-derived polycarboxylic acid and polyethylene terephthalate is reacted in the presence of a titanium compound.
- a method for producing a polyester resin comprising a reaction step and a step of polycondensing the reaction product obtained in the reaction step, The carbon atom ratio derived from the polyethylene terephthalate is 5 to 40% with respect to the total carbon atom weight of the raw material, and at least part of the reaction step is performed at a temperature equal to or higher than the melting point of polyethylene terephthalate. Production method.
- the present invention has the following aspects.
- [1-1] Containing a structural unit derived from polyethylene terephthalate and a structural unit derived from a polyhydric alcohol containing isosorbide, the carbon atom ratio derived from the polyethylene terephthalate is 5 to 40%, and the methyl ethyl ketone insoluble content is 5% by mass or less
- the polyester resin according to [1-1] which contains a structural unit derived from a polycarboxylic acid.
- At least a portion of at least one of the polyethylene terephthalate-derived structural units and the polyhydric alcohol-derived structural units containing the isosorbide is derived from biomass, and the biomass-derived carbon atom ratio is the polyester resin 1 to 95% of the total carbon atoms contained in the polyester resin according to any one of [1-1] to [1-3].
- At least a portion of at least one of the structural units derived from polyethylene terephthalate, the structural units derived from the polyhydric alcohol containing the isosorbide, and the structural units derived from the polycarboxylic acid is derived from biomass, and
- the present invention has the following aspects.
- a method for producing a polyester resin comprising a step of reacting a raw material mixture containing polyethylene terephthalate and a biomass-derived monomer, wherein the carbon atom ratio derived from the biomass-derived monomer is the total carbon atoms in the raw material mixture. 30.0 to 90.0% of the biomass-derived monomer, wherein the biomass-derived monomer contains at least erythritan.
- the present invention it is possible to provide a polyester resin with good solvent solubility and light color that can be used for light-colored inks and paints, a method for producing the same, paints, inks, adhesives, and image-forming materials. can be done.
- the polyester resin of the first aspect of the present invention comprises structural units derived from at least one of biomass-derived polyhydric alcohols and biomass-derived polycarboxylic acids, and polyethylene terephthalate (hereinafter also referred to as “PET”). ), the ratio of carbon atoms derived from polyethylene terephthalate is 5 to 40% with respect to 100% of all carbon atoms, and the methyl ethyl ketone insoluble content is 5% by mass or less.
- PET polyethylene terephthalate
- the polyester resin of one embodiment of the present invention uses, as raw materials, a mixture M containing PET and at least one of a biomass-derived polyhydric alcohol component and a biomass-derived polycarboxylic acid component.
- the mixture M may contain PET, a polyhydric alcohol component that is at least one of biomass-derived isosorbide and erythritan, and a biomass-derived polycarboxylic acid component. That is, the polyester resin is the reaction product of mixture M. At least part of the monomers contained in the mixture M are biomass-derived monomers.
- Mixture M may include petroleum-derived monomers.
- a "biomass-derived monomer” refers to a monomer produced using a plant as a raw material. The carbon atoms that make up the biomass-derived monomer are of plant origin.
- “Petroleum-derived monomer” refers to a monomer produced from petroleum as a raw material, excluding PET and biomass-derived monomers. The carbon atoms that make up the petroleum-derived monomer are derived from petroleum.
- PET for example, those produced according to conventional methods by esterification or transesterification of ethylene glycol and terephthalic acid, dimethyl terephthalate, etc., and polycondensation can be used.
- unused PET may be used, or recycled PET obtained by regenerating (that is, recycling) used PET or PET products may be used.
- PET using biomass-derived raw materials may be used as PET, and A-PET (amorphous polyethylene terephthalate), C-PET (crystalline polyethylene terephthalate), and G-PET (glycol-modified polyethylene terephthalate) are used.
- A-PET amorphous polyethylene terephthalate
- C-PET crystalline polyethylene terephthalate
- G-PET glyco-modified polyethylene terephthalate
- the recycled PET may be obtained by processing used PET into pellets, or may be obtained by crushing products such as films and bottles, or scraps.
- Examples of PET using a biomass-derived raw material include PET in which at least one of ethylene glycol and terephthalic acid is derived from biomass. Whether or not PET uses a biomass-derived raw material can be confirmed by, for example, ASTM D6866 "Standard for determination of biogenic carbon concentration using radiocarbon (C14) measurement method". Recycled PET or PET using a biomass-derived raw material is preferable as PET from the viewpoint of environmental conservation. PET using a biomass-derived raw material may be unused or used. PET may be used individually by 1 type, and may use 2 or more types together.
- the content of PET-derived carbon atoms ie, the carbon atom ratio of the PET-derived carbon atoms, is 5 to 40% with respect to the total carbon atoms in the mixture M.
- an ethylene skeleton derived from ethylene glycol and a benzene ring having a functional group at the para position derived from terephthalic acid or its lower alkyl ester are ester-bonded. Therefore, if PET is partially used and polymerized together with the polyhydric carboxylic acid component and the polyhydric alcohol component, a random polymer is rapidly formed by the transesterification reaction.
- the ratio of carbon atoms derived from PET By setting the ratio of carbon atoms derived from PET to 5% or more of the total carbon atoms in the mixture M, it is possible to contribute to shortening the polymerization time and to suppress coloration of the resin due to heating during polymerization. Further, by setting the content of carbon atoms derived from PET to 40% or less of the total carbon atoms in the mixture M, the resulting polyester resin has good solvent solubility.
- the content of carbon atoms derived from PET is more preferably 30% or less, more preferably 5 to 30%, based on the total carbon atoms in the mixture M.
- the ratio of PET-derived carbon atoms to the total carbon atoms in the mixture M can be calculated based on the number of carbon atoms and molar ratio of each component constituting the mixture M.
- the carbon atom ratio derived from isosorbide, the carbon atom ratio derived from erythritan, and the carbon atom ratio of biomass-derived monomers, which will be described later,
- the IV (Intrinsic Viscosity) value of PET that can be used in the present invention is preferably 0.2 to 1.2, more preferably 0.3 to 1.1, from the viewpoint of controlling the crystallinity of the obtained polyester resin, and 0.3 to 1.1. 4 to 0.8 is more preferred, and 0.4 to 0.6 is most preferred.
- the IV value of PET was obtained by dissolving 0.3 g of PET in 30 mL of a mixed solvent in which phenol and 1,1,2,2-tetrachloroethane were mixed at a mass ratio of 1:1, and measuring the resulting solution with an Ubbelohde viscometer. It is a value measured at 30°C using
- biomass-derived polyvalent carboxylic acids include divalent carboxylic acids and trivalent or higher carboxylic acids.
- divalent carboxylic acids include isomers of terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid (specifically 1,4-, 1,5-, 1,6-, 1,7-, 2,5- , 2,6-, 2,7-, 2,8-), and aromatic dicarboxylic acids such as lower alkyl esters or acid anhydrides thereof; succinic acid, isodecylsuccinic acid, dodecenylsuccinic acid, maleic acid, fumaric acid , adipic acid, sebacic acid, 2,5-furandicarboxylic acid, and aliphatic dicarboxylic acids such as lower alkyl esters or acid anhydrides thereof.
- lower alkyl esters of terephthalic acid and isophthalic acid examples include dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate and dibutyl isophthalate.
- polyvalent carboxylic acids containing heterocycles are preferred as divalent carboxylic acids.
- terephthalic acid, isophthalic acid, adipic acid, 2,5-furandicarboxylic acid and succinic acid are preferred, and 2,5-furandicarboxylic acid and succinic acid are more preferred, from the viewpoint of excellent handleability and cost.
- Divalent carboxylic acids may be used alone or in combination of two or more. It may also be used in combination with a trivalent or higher carboxylic acid, which will be described later.
- Trivalent or higher carboxylic acids include, for example, trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1, 2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, and their acid anhydrides and lower alkyl esters.
- the trivalent or higher carboxylic acid is preferably trimellitic acid, trimellitic anhydride, pyromellitic acid, or pyromellitic anhydride in terms of excellent handling and cost. are particularly preferred.
- the carboxylic acids having a valence of 3 or more may be used singly or in combination of two or more.
- biomass-derived polyhydric alcohol components include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin, isosorbide, isomannide, erythritane, sorbitol, erythritol and the like. It is preferably a hydric alcohol component. More preferably, the biomass-derived polyhydric alcohol component is at least one of isosorbide and erythritan.
- Isosorbides include D-isosorbide and L-isosorbide.
- the content of carbon atoms contained in isosorbide-derived structural units in the polyester resin is preferably 1 to 30% of the total carbon atoms contained in the polyester resin. It is preferable to use 1% or more of carbon atoms contained in structural units derived from isosorbide from the viewpoint of reducing environmental load, and it is effective in increasing the glass transition temperature (also referred to as Tg) of the polyester resin.
- Tg glass transition temperature
- the content of carbon atoms contained in structural units derived from isosorbide is more preferably 5 to 25%.
- Erythritan is preferably erythritan (1,4-anhydroerythritol), a biomass-derived monomer synthesized by an intramolecular dehydration reaction of erythritol, a natural polysaccharide.
- the ratio of carbon atoms derived from erythritan in the polyester resin is preferably 5 to 35% with respect to the total carbon atoms constituting the polyester resin. If the ratio of carbon atoms derived from erythritan is 5% or more, it is preferable from the standpoint of reducing environmental load, and has the effect of increasing the glass transition temperature (also referred to as Tg) of the polyester resin. Moreover, when the carbon atom ratio derived from erythritan is 35% or less, the obtained polyester resin tends to have good solvent solubility.
- the ratio of carbon atoms derived from erythritan is more preferably 8 to 28% with respect to the total carbon atoms constituting the polyester resin.
- Polyhydric alcohol components include dihydric alcohols other than isosorbide and erythritan (hereinafter also referred to as “other dihydric alcohols”) and trihydric or higher alcohols (also referred to as “other trihydric alcohols”). may contain.
- dihydric alcohols include, for example, ethylene glycol, neopentyl glycol, propylene glycol, hexanediol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4 -aliphatic alcohols such as cyclohexanedimethanol, isomannide, and 1,4-dihydroxy-2-butene, such as polyoxypropylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxy Propylene-(2.2)-2,2-bis(4-hydroxyphenyl)propane, Polyoxypropylene-(2.3)-2,2-bis(4-hydroxyphenyl)propane, Polyoxypropylene-(2 .4)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2,2-bis(4-hydroxyphenyl)propane polyoxypropylene (6)-2,
- dihydric alcohols may be used singly or in combination of two or more. Further, it may be derived from petroleum or biomass.
- ethylene is the average number of added moles of ethylene oxide
- propylene is the average number of added moles of propylene oxide.
- trihydric or higher alcohols examples include trimethylolpropane, sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, and 1,2,5-pentanetriol. , glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, 1,3,5-trihydroxymethylbenzene and glycerin.
- Other trihydric or higher alcohols may be used alone or in combination of two or more. Moreover, it may be derived from petroleum or biomass.
- the ratio of carbon atoms derived from biomass-derived monomers in the polyester resin is preferably 1 to 95% of the total carbon atoms contained in the mixture M. If the ratio of carbon atoms derived from biomass-derived monomers is 1% or more, the effect of reducing the amount of petroleum-derived monomers used can be enhanced. Further, when the carbon atom ratio derived from the biomass-derived monomer is 95% or less, the obtained polyester resin tends to have good storage stability and solvent solubility.
- the ratio of biomass-derived carbon atoms to the total carbon atoms contained in the polyester resin is preferably 1 to 95%, may be 2 to 85%, or may be 3 to 70%.
- the carbon atom ratio derived from the biomass-derived polyhydric alcohol, the biomass-derived polycarboxylic acid and the polyethylene terephthalate is 6 to 100 with respect to the total carbon atoms contained in the polyester resin. %, more preferably 10 to 100%.
- the mixture M may contain components other than the PET, the polyhydric carboxylic acid component and the polyhydric alcohol component (hereinafter also referred to as other components). That is, the polyester resin may contain structural units derived from other components.
- Other components include monovalent carboxylic acids, monovalent alcohols and monoesters of monovalent carboxylic acids and monovalent alcohols. Examples of monovalent carboxylic acids include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid; aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid; cinnamic acid and olein.
- Acids unsaturated carboxylic acids having one or more double bonds in the molecule such as linoleic acid and linolenic acid, and the like.
- monohydric alcohols include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol; and aliphatic alcohols having 30 or less carbon atoms such as oleyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol.
- monoesters of monohydric alcohols and monocarboxylic acids include natural ester waxes such as carnauba wax and rice wax. Other components may be derived from petroleum or biomass, but are more preferably derived from biomass.
- the polyester resin of the present embodiment has an MEK-insoluble content of 5% by mass or less.
- the MEK-insoluble content is preferably as small as possible, most preferably 0% by mass. If the MEK-insoluble matter is 5% by mass or less, the suitability for solvent-based inks, paints, etc., and applications in which the composition is dissolved in a solvent is enhanced.
- solvent solubility is essential when emulsifying by a phase inversion emulsification method, etc., and 5 mass % or less, the aptitude increases.
- the polyester resin of the first aspect of the present invention preferably has an L value of 40 or more and an a value of +2.4 or less.
- the L value and the a value were measured by sieving a polyester resin having a particle size of 1 to 2 mm and using a spectrophotometer (for example, CM-5 manufactured by Konica Minolta Co., Ltd.) at a field of view of 2°. , is the Hunter Lab value.
- the L value indicates lightness and ranges from black (0) to white (100). A larger value indicates a higher brightness.
- the a value takes a positive value when red is strong, and takes a negative value when green is strong.
- the polyester resin of the first aspect of the present application is a resin that has high brightness and suppressed redness even when isosorbide, which tends to be colored brown, is copolymerized.
- the polyester resin of the present invention is preferably a uniform solution in both a solution in which the solid content is 30% by mass in MEK and a solution in which the solid content is 40% by mass in MEK.
- a uniform MEK solution will enhance suitability for solvent-based inks, paints, etc., and applications where the solution is dissolved in a solvent.
- solvent solubility is essential when emulsifying by a phase inversion emulsification method, etc., and emulsification suitability increases.
- the term "homogeneous solution” refers to a state in which no separation of the liquid phase is observed when the solution is allowed to stand, and no or very little precipitates are observed.
- the Tg of the polyester resin is preferably 30° C. or higher, more preferably 40° C. or higher, and even more preferably 50° C. or higher, from the viewpoint of storage stability of the polyester resin. Moreover, from the viewpoint of ease of melting, the Tg of the polyester resin is preferably 100° C. or lower, and may be 80° C. or lower. The upper limit and lower limit of the preferred range of Tg of the polyester resin can be combined arbitrarily. For example, Tg of the polyester resin is preferably 30 to 100°C.
- the glass transition temperature of the polyester resin is obtained as follows.
- the softening temperature (also referred to as T4) of the polyester resin is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher, from the viewpoint of storage stability of the resin. Moreover, from the viewpoint of ease of melting, the temperature is preferably 170° C. or lower, more preferably 150° C. or lower.
- the upper limit and lower limit of T4 of the polyester resin can be combined arbitrarily.
- the T4 of the polyester resin is preferably 90 to 170°C, more preferably 90 to 170°C, even more preferably 100 to 150°C.
- the softening temperature of the polyester resin is obtained as follows. That is, using a flow tester (for example, "CFT-500D” manufactured by Shimadzu Corporation), a nozzle of 1 mm ⁇ ⁇ 10 mm, a load of 294 N (30 kgf), a temperature increase rate of 3 ° C. / min. Then, the temperature at which 1/2 of 1.0 g of the polyester resin flows out is measured and taken as the softening temperature.
- a flow tester for example, "CFT-500D” manufactured by Shimadzu Corporation
- a nozzle of 1 mm ⁇ ⁇ 10 mm a load of 294 N (30 kgf)
- a temperature increase rate of 3 ° C. / min.
- the acid value (also referred to as AV) of the polyester resin is preferably 1 to 40 mgKOH/g, more preferably 3 to 30 mgKOH/g. If the acid value of the polyester resin is at least the above lower limit, the productivity of the polyester resin is improved. If the acid value of the polyester resin is equal to or less than the above upper limit, the moisture resistance of the polyester resin is improved, and it becomes less susceptible to the use environment. Incidentally, when the acid value of the polyester resin is in the range of approximately 6 to 15 mgKOH/g, neutralization phase inversion emulsification becomes possible and it is suitable for use as an emulsion.
- the acid value of the polyester resin is expressed in milligrams as the amount of potassium hydroxide required to neutralize the carboxyl groups per 1 g of the sample, and is expressed in units of mgKOH/g.
- the acid value of the polyester resin is a value obtained by dissolving the polyester resin in benzyl alcohol and titrating with a 0.02 N KOH solution using cresol red as an indicator.
- the hydroxyl value (also referred to as OHV) of the polyester resin is preferably 10-70 mgKOH/g, more preferably 10-50 mgKOH/g. If the hydroxyl value of the polyester resin is at least the above lower limit, the productivity of the polyester resin is improved. When the hydroxyl value of the polyester resin is equal to or less than the above upper limit, the moisture resistance of the polyester resin is improved, and it becomes less susceptible to the use environment.
- the hydroxyl value of the polyester resin is expressed in milligrams as the amount of potassium hydroxide corresponding to the number of hydroxyl groups per 1 g of the sample, and is expressed in units of mgKOH/g.
- the hydroxyl value of the polyester resin is obtained by dissolving the polyester resin in tetrahydrofuran, reacting it with acetic anhydride in the presence of dimethylaminopyridine to acetylate the hydroxyl group, hydrolyzing the excess acetic anhydride to acetic acid, and then adding phenolphthalein. is titrated using a 0.5 N KOH solution as an indicator and calculated from the consumption of acetic anhydride.
- the particle size of the emulsion after phase inversion emulsification is preferably 50 to 500 nm, more preferably 60 to 300 nm.
- the particle size of the emulsion after phase inversion emulsification is 50 to 500 nm, the stability of the emulsion tends to be good, and it can be suitably used for water-based inks and coatings.
- the particle size of the emulsion is measured using the emulsion obtained by the following phase inversion emulsification method.
- the polyester resin is dissolved in 3 times the amount of MEK as the polyester resin, and an amount of base capable of neutralizing 100% or more of the carboxylic acid of the polyester resin is added to the beaker and thoroughly blended.
- bases aqueous ammonia, dimethylaminoethanol, sodium hydroxide, potassium hydroxide, and the like can be appropriately used.
- four times as much pure water as the polyester resin is added to the round-bottomed flask, and the above MEK solution is added thereto, followed by treatment with a homogenizer at 8000 rpm for 10 minutes.
- a flask cover, a stirring blade and a cooling pipe are attached, and the pressure is reduced by an aspirator while being heated to 70°C in a water bath to distill off MEK to obtain an emulsion consisting only of water and resin.
- the particle diameter is measured using a laser diffraction/scattering particle size distribution analyzer (LA-960, manufactured by Horiba, Ltd.), and the median diameter (also referred to as D50 ) is taken as the particle diameter of the emulsion.
- a raw material containing at least one of a biomass-derived polyhydric alcohol and a biomass-derived polycarboxylic acid, and polyethylene terephthalate in the presence of a titanium compound.
- a method for producing a polyester resin comprising a reaction step that is at least one of an esterification reaction and a transesterification reaction to be reacted, and a step of polycondensing the reaction product obtained in the reaction step, wherein carbon derived from polyethylene terephthalate
- the atomic ratio is 5 to 40% with respect to the total carbon atom weight of the raw material, and at least part of the reaction step is performed at a temperature equal to or higher than the melting point of polyethylene terephthalate.
- the method for producing a polyester resin of the present embodiment includes a step of reacting a mixture M, which is a raw material containing at least one of the above-described biomass-derived polyhydric alcohol and biomass-derived polycarboxylic acid, and polyethylene terephthalate. include.
- the ratio of carbon atoms derived from PET to the total carbon atom weight of the mixture M, ie the raw material, is 5-40%.
- the ratio of carbon atoms derived from biomass-derived monomers in the mixture M is preferably 1 to 95%, more preferably 2 to 85%, and even more preferably 3 to 70%, based on the total carbon atoms derived from the mixture M.
- the ratio of PET-derived carbon atoms in the mixture M is more preferably 5 to 30% with respect to the total carbon atoms derived from the mixture M.
- the ratio of carbon atoms derived from erythritan is preferably 5 to 35%, more preferably 8 to 28%, relative to the total carbon atoms derived from the raw material mixture M.
- the isosorbide-derived carbon atom ratio is preferably 1 to 30%, more preferably 5 to 25%, relative to the total carbon atoms derived from the raw material mixture M.
- the step of reacting the mixture M it is preferable to carry out a polycondensation reaction after carrying out at least one of the esterification reaction and the transesterification reaction.
- the mixture M and a catalyst such as a titanium compound, are put into a reaction vessel, heated to raise the temperature, and at least one of an esterification reaction and a transesterification reaction is performed, and water or alcohol produced in the reaction is removed. .
- the polycondensation reaction is continued.
- the pressure inside the reactor is gradually reduced, and the polyhydric alcohol component is distilled under a pressure of 150 mmHg (that is, 20 kPa) or less, preferably 15 mmHg (that is, 2 kPa) or less.
- titanium-based compounds are used from the viewpoint of safety as catalysts used during the esterification reaction, the transesterification reaction, and the polycondensation reaction.
- titanium-based compounds include titanium alkoxide compounds having an alkoxy group, titanium carboxylate, titanyl carboxylate, titanyl carboxylate, and titanium chelate compounds.
- Titanium alkoxide compounds having an alkoxy group include, for example, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentoxytitanium and tetraoctoxytitanium.
- titanium carboxylate compounds include titanium formate, titanium acetate, titanium propionate, titanium octanoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, titanium sebacate, titanium hexanetricarboxylate, and isooctanetricarboxylic acid.
- tetrabutoxytitanium is particularly preferable because of its availability and the like.
- One of the above catalysts may be used alone, or two or more thereof may be used in combination.
- the polymerization temperature in the esterification reaction or transesterification reaction is higher than the melting point of PET from the viewpoint of shortening the reaction time.
- the melting point of PET is around 255°C.
- the polymerization temperature in the esterification reaction or transesterification reaction is preferably 260° C. or higher, more preferably 265° C. or higher.
- the upper limit of the polymerization temperature in the esterification reaction or transesterification reaction is preferably 290° C. or lower, more preferably 280° C. or lower.
- the polymerization temperature during the polycondensation reaction is preferably 180 to 280°C, more preferably 200 to 270°C, and particularly preferably 210 to 255°C.
- the productivity of the polyester resin is improved. If the polymerization temperature is equal to or lower than the above upper limit, decomposition of the polyester resin and by-production of volatile matter that causes odor can be suppressed, and TVOC (Total Volatile Organic Compounds) can be reduced.
- the esterification reaction and/or transesterification reaction time is preferably within 3 hours.
- water or a lower alcohol is distilled from the reaction system along with the reaction. It means the time from the start of distillation to the end of distillation.
- the polymerization end point is determined, for example, by the softening temperature of the polyester resin.
- the polymerization may be terminated after the polycondensation reaction is performed until the torque of the stirring blade reaches a value indicating the desired softening temperature.
- “to terminate the polymerization” means to stop agitation of the reaction vessel and introduce nitrogen into the interior of the reaction vessel to make the inside of the vessel normal pressure.
- the polycondensation reaction time is the time from when the reaction system is brought to the polycondensation reaction temperature and pressure reduction is started until the polymerization is completed. After cooling, the resulting polyester resin may be ground to a desired size.
- the polyester resin of the first aspect of the present invention described above is a polyester resin having good solvent solubility and light color, while considering environmental and safety aspects by reducing the amount of petroleum-derived raw materials used. Therefore, it can also be used for applications such as light-colored inks and paints.
- the polyester resin of the first aspect of the present invention uses PET as a part of raw materials. Since PET already contains structural units derived from ethylene glycol, the polyester resin of the first aspect of the present invention can reduce the amount of ethylene glycol used as a raw material monomer. Ethylene glycol is a VOC (volatile organic compound), and if unreacted ethylene glycol remains in the polyester resin, the ethylene glycol volatilizes when heat is applied, causing an odor. However, with the polyester resin of the first aspect of the present invention, the amount of ethylene glycol used can be reduced, so the TVOC can be reduced and the odor can be suppressed. Since ethylene glycol as a monomer does not generally remain in PET, VOC derived from PET is unlikely to occur.
- VOC volatile organic compound
- the polyester resin of the first aspect of the present invention includes solvent-based inks and paints, water-based inks and paints, powder paints, toners, solvent-based liquid developers, water-based developers, adhesives, image-forming materials, and the like. can be widely used for
- a polyester resin having good solvent solubility and a light color can be produced while considering the environment and safety by reducing the amount of petroleum-derived raw materials used. Easy to manufacture. Moreover, since PET is used as a part of the raw material of the polyester resin, the PET serves as a starting point, and the esterification reaction and the transesterification reaction easily proceed, so that the reaction time can be shortened.
- the glass transition temperature of the polyester resin was measured using a differential scanning calorimeter ("DSC-60" manufactured by Shimadzu Corporation), and the intersection point between the baseline of the chart and the tangent line of the endothermic curve at a heating rate of 5 ° C./min. measured from 10 mg ⁇ 0.5 mg of the sample was weighed into an aluminum pan, melted at 100° C. for 10 minutes, and then rapidly cooled using dry ice. Furthermore, based on the measurement results, the storage stability was evaluated according to the following criteria. (Evaluation criteria) A: Tg is 50°C or higher. ⁇ : Tg is 30°C or more and less than 50°C. x: Tg is less than 30°C.
- the softening temperature of the polyester resin was measured using a flow tester (manufactured by Shimadzu Corporation, "CFT-500D") with a nozzle of 1 mm ⁇ ⁇ 10 mm, a load of 294 N, and a constant heating rate of 3 ° C./min. The temperature at which 1/2 of the resin sample (1.0 g) flowed out was measured and taken as the softening temperature.
- the hydroxyl value of the polyester resin was measured as follows. About 5 g of a measurement sample was accurately weighed in an Erlenmeyer flask (a (g)), 50 mL of tetrahydrofuran was added, and the sample was stirred and dissolved with a stirrer. Then, 30 mL of a solution prepared by dissolving 5.000 g of dimethylaminopyridine in tetrahydrofuran and adjusting the volume to 500 mL was added to the Erlenmeyer flask.
- the molecular weight of the polyester resin was determined as a polystyrene-equivalent value by the GPC method under the following conditions.
- Apparatus HLC8020 manufactured by Tosoh Corporation Column: TSKgelGMHXL (column size: 7.8 mm (ID) ⁇ 30.0 cm (L)), manufactured by Tosoh Corporation, connected in series with 3 columns Oven temperature: 40 ° C.
- Example 1 ⁇ Production of polyester resin> Per 100 mol parts of the acid component, 34 mol parts (159.2 g) of PET-1, 60 mol parts (242.9 g) of terephthalic acid, 6 mol parts (28.1 g) of trimellitic anhydride, and polyoxy 65 mol parts (570.1 g) of propylene-(2.3)-2,2-bis(4-hydroxyphenyl)propane, 20 mol parts (71.2 g) of isosorbide, and tetrabutoxytitanium as a catalyst were used as acid components. 500 ppm (0.215 g) was added to a reaction vessel equipped with a distillation column.
- PET-1 is defined as 1 mol of PET-1, which is a unit composed of 1 mol of terephthalic acid and 1 mol of ethylene glycol, and 1 mol of PET-derived terephthalic acid per 1 mol of PET-1 is expressed as 1 mol of the acid component.
- PET-derived ethylene glycol was counted as 1 mol of the alcohol component.
- the isosorbide used was a biomass-derived raw material.
- the temperature in the reaction system was lowered and maintained at 235°C, the pressure in the reaction vessel was reduced over about 20 minutes, and the degree of vacuum was set to 133 Pa to carry out a polycondensation reaction.
- the viscosity of the reaction system increased with the reaction, the degree of vacuum was increased as the viscosity increased, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating the desired softening temperature.
- stirring was stopped, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reactant was taken out from the reaction vessel to obtain a polyester resin.
- the time required for the polycondensation reaction (that is, the polycondensation reaction time) is shown in Table 1 as "polycondensation reaction".
- the polyester resin obtained in Example 1 includes structural units derived from terephthalic acid, structural units derived from trimellitic anhydride, and polyoxypropylene-(2.3)-2,2-bis(4-hydroxyphenyl). It contains propane-derived structural units, isosorbide-derived structural units, and ethylene glycol-derived structural units, and the ratio of each structural unit generally matches the charged composition. That is, the polyester resin obtained in Example 1 contained 14.1% of carbon atoms derived from PET and 5.0% of carbon atoms derived from isosorbide.
- Example 2-6 Comparative Examples 1-2
- ⁇ Production of polyester resin> A polyester resin was produced in the same manner as in Example 1, except that the charge composition, esterification reaction time and/or transesterification reaction time and polycondensation reaction time shown in Table 1 were changed, and various measurements and evaluations were performed.
- biomass-derived succinic acid, propylene glycol, and glycerin were used in addition to isosorbide. These results are shown in Table 1.
- PET-2 instead of PET-1, PET-2, which is recycled polyethylene terephthalate having an IV value of 0.73, which is obtained by regenerating used PET containing a small amount of structural units derived from isophthalic acid, was used.
- polyester resin 20 mol parts (100.0 g) of PET-1, 30 mol parts (129.7 g) of isophthalic acid, 50 mol parts (153.6 g) of succinic acid, 40 mol parts (79.2 g) of propylene glycol, 45 mol parts (121.9 g) of erythritan and 500 ppm (0.192 g) of tetrabutoxytitanium as a catalyst with respect to the acid component were charged into a reactor equipped with a distillation column.
- the raw material mixture M charged into the reaction vessel in Example 7 contained 100 mol parts of the acid component and 105 mol parts of the alcohol component.
- succinic acid, propylene glycol, and erythritan were derived from biomass.
- the rotation speed of the stirring blade in the reaction vessel was kept at 200 rpm, and the temperature was started to rise.
- the temperature inside the reaction system was heated to 265°C, and the esterification reaction was carried out while this temperature was maintained.
- the esterification reaction was terminated when no more water was distilled from the reaction system.
- the temperature in the reaction system was lowered and maintained at 235°C, the pressure in the reaction vessel was reduced over about 20 minutes, and the degree of vacuum was set to 133 Pa to carry out a polycondensation reaction.
- the viscosity of the reaction system increased with the reaction, the degree of vacuum was increased as the viscosity increased, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating the desired softening temperature.
- stirring was stopped, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reactant was taken out from the reaction vessel to obtain a polyester resin.
- the glass transition temperature, softening temperature, acid value, L value, a value, MEK insoluble matter, hydroxyl value, weight average molecular weight, number average molecular weight, and weight average molecular weight/number average molecular weight of the resulting polyester resin were measured. These results are shown in Table 2 as Tg, T4, AV, L, a, MEK insolubles, OHV, Mw, Mn and Mw/Mn, respectively.
- the polyester resin obtained in Example 7 includes structural units derived from terephthalic acid, structural units derived from isophthalic acid, structural units derived from succinic acid, structural units derived from propylene glycol, structural units derived from erythritan, and structural units derived from ethylene glycol.
- the polyester resin obtained in Example 7 contains 21.3% PET-derived carbon atoms, 19.1% erythritan-derived carbon atoms, and erythritan, relative to the total carbon atoms constituting the polyester resin. It contained 53.2% carbon atoms derived from biomass-derived monomers and 25.5% carbon atoms derived from petroleum-derived raw materials.
- Emulsions were produced from the polyester resins obtained in Examples 4, 9 and 10.
- a polyester resin was dissolved in 75 g of MEK, and dimethylaminoethanol in an amount capable of neutralizing 120% of the carboxylic acid of the polyester resin was added into the beaker and thoroughly blended.
- 100 ml of pure water was put into a 300 ml round-bottomed flask, and the above MEK solution was put therein and treated with a homogenizer at 8000 rpm for 10 minutes.
- Tables 1 and 2 Abbreviations in Tables 1 and 2 are as follows. A blank column in the column of monomer composition in the table means that the component is not blended (the blending amount is 0% by mass or 0 mol part).
- ⁇ TPA terephthalic acid
- IPA isophthalic acid
- TMA trimellitic anhydride
- Bio-ScA biomass-derived succinic acid
- Bio-FDCA biomass-derived 2,5-furandicarboxylic acid
- BPP polyoxypropylene-(2.
- Bio-EG biomass-derived ethylene glycol
- Bio-PG biomass-derived propylene glycol
- (1,2-propanediol) biomass-derived
- Bio-GLY biomass Derived glycerin
- Bio-isosorbide biomass-derived isosorbide, PSA grade manufactured by Rocket Co., Ltd.
- Bio-erythritan biomass-derived erythritan
- PET-1 Recycled polyethylene terephthalate with an IV value of 0.57, which is recycled from used
- PET-2 Recycled polyethylene terephthalate with an IV value of 0.73, which is recycled from used PET containing a small amount of structural units derived from isophthalic acid
- the IV value of PET is the sum of phenol and 1,1,2,2-tetrachloroethane 0.3 g of PET was dissolved in 30 mL of a mixed solvent mixed at a mass ratio of 1:1, and the resulting solution was measured at 30° C. using an Ubbelohde viscometer.
- the polyester resin obtained in each example is a polyester resin with a low carbon atom ratio derived from petroleum-derived monomers and with reduced environmental load, and has good solvent solubility and lightness. It was a polyester resin with high and low redness. Moreover, it was confirmed that an emulsion can be obtained by the phase inversion emulsification treatment. Such polyester resins are also suitable for use in water-based inks and coatings and the like.
- the polyester resin of Comparative Example 1 in which PET was not used, took a long time for the esterification reaction and/or the transesterification reaction, and was a resin with strong redness.
- the polyester resin of the present invention is a light-colored polyester resin that has good solvent solubility while taking into account environmental and safety aspects, and is also useful for light-colored inks and paints.
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Abstract
Description
本願は、2021年3月22日に日本に出願された特願2021-047375号及び2021年9月22日に日本に出願された特願2021-154388ついて優先権を主張し、その内容をここに援用する。
[1] バイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種に由来する構成単位、及びポリエチレンテレフタレート由来の構成単位を含み、全炭素原子100%に対して前記ポリエチレンテレフタレート由来の炭素原子比率が5~40%であり、メチルエチルケトン不溶分が5質量%以下である、ポリエステル樹脂。
[2] 前記バイオマス由来の多価アルコールに由来する構成単位が、ヘテロ環を含む多価アルコールに由来する構成単位である、[1]に記載のポリエステル樹脂。
[3]前記バイオマス由来の多価アルコールがイソソルバイド及びエリスリタンの少なくとも1種である、[1]又は[2]に記載のポリエステル樹脂。
[4] 前記バイオマス由来の多価カルボン酸に由来する構成単位が、ヘテロ環を含む多価カルボン酸に由来する構成単位である、[1]~[3]のいずれか1項に記載のポリエステル樹脂。
[5]前記バイオマス由来の多価カルボン酸がコハク酸及び2,5-フランジカルボン酸の少なくとも1種である、[1]~[4]のいずれか1項に記載のポリエステル樹脂。
[6] 前記バイオマス由来の多価アルコール及び前記バイオマス由来の多価カルボン酸由来の炭素原子比率が、前記ポリエステル樹脂に含まれる全炭素原子に対し、1~95%である、[1]~[5]のいずれか1項に記載のポリエステル樹脂。
[7] 前記バイオマス由来の多価アルコール、前記バイオマス由来の多価カルボン酸及び前記ポリエチレンテレフタレート由来の炭素原子比率が、前記ポリエステル樹脂に含まれる全炭素原子に対し、6~100%である、[1]~[6]のいずれか1項に記載のポリエステル樹脂。
[8] 篩い分けにて粒径1~2mmの前記ポリエステル樹脂を分取し、分光測色計にて測定した場合のL値が40以上であり、a値が2.4以下である、[1]~[8]のいずれか1項に記載のポリエステル樹脂。
[9] [1]~[8]のいずれか1項に記載のポリエステル樹脂、及び溶剤を含む塗料。
[10] [1]~[8]のいずれか1項に記載のポリエステル樹脂を含むインク。
[11] [1]~[8]のいずれか1項に記載のポリエステル樹脂を含む粘接着材。
[12] [1]~[8]のいずれか1項に記載のポリエステル樹脂を含む画像形成材。
[13] バイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種、及びポリエチレンテレフタレートを含む原料を、チタン化合物の存在下で反応させるエステル化反応及びエステル交換反応の少なくとも一方である反応工程と、前記反応工程で得られた反応物を重縮合する工程とを含むポリエステル樹脂の製造方法であって、
前記ポリエチレンテレフタレートに由来する炭素原子比率が、前記原料の全炭素原子量に対して5~40%であり、前記反応工程の少なくとも一部が、ポリエチレンテレフタレートの融点以上の温度で行われる、ポリエステル樹脂の製造方法。
[14] 前記バイオマス由来の多価アルコールが、ヘテロ環を含む多価アルコールである、[13]に記載の製造方法。
[15] 前記バイオマス由来の多価アルコールがイソソルバイド及びエリスリタンの少なくとも1種である、[14]に記載の製造方法。
[16] 前記バイオマス由来の多価カルボン酸が、ヘテロ環を含む多価カルボン酸である、[13]に記載の製造方法。
[17] 前記バイオマス由来の多価カルボン酸がコハク酸及び2,5-フランジカルボン酸の少なくとも1種である、[16]に記載の製造方法。
[18] 前記反応工程が3時間以内である、[14]~[17]のいずれか1項に記載の製造方法。
[1-1] ポリエチレンテレフタレート由来の構成単位、及びイソソルバイドを含む多価アルコール由来の構成単位を含み、前記ポリエチレンテレフタレート由来の炭素原子比率が5~40%であり、メチルエチルケトン不溶分が5質量%以下であり、L値が40以上であり、a値が2.4以下である、ポリエステル樹脂。
[1-2] 多価カルボン酸由来の構成単位を含む、[1-1]に記載のポリエステル樹脂。
[1-3] 前記イソソルバイド由来の炭素原子比率が、前記ポリエステル樹脂に含まれる全炭素原子に対し、1~30%である、[1-1]又は[1-2]に記載のポリエステル樹脂。
[1-4] 前記ポリエチレンテレフタレート由来の構成単位及び前記イソソルバイドを含む多価アルコール由来の構成単位の少なくとも一方のうちの少なくとも一部がバイオマス由来であり、前記バイオマス由来の炭素原子比率が前記ポリエステル樹脂に含まれる全炭素原子に対し、1~95%である、[1-1]~[1-3]のいずれか1つに記載のポリエステル樹脂。
[1-5]前記ポリエチレンテレフタレート由来の構成単位、前記イソソルバイドを含む多価アルコール由来の構成単位及び前記多価カルボン酸由来の構成単位の少なくとも1つのうちの少なくとも一部がバイオマス由来であり、前記バイオマス由来の炭素原子比率が前記ポリエステル樹脂に含まれる全炭素原子に対し、1~95%である、[1-2]又は[1-3]に記載のポリエステル樹脂。
[1-6] [1-1]~[1-5]に記載のポリエステル樹脂、及び溶剤を含む塗料。
[1-7] ポリエチレンテレフタレート、及びイソソルバイドを含む多価アルコールを含む原料を、チタン化合物の存在下で反応させるエステル化工程と、前記エステル化工程で得られた反応物を重縮合する工程とを含むポリエステル樹脂の製造方法であって、前記ポリエチレンテレフタレート由来の炭素原子比率が、前記原料の全炭素原子量に対して5~40%であり、前記エステル化工程の少なくとも一部が、ポリエチレンテレフタレートの融点以上の温度で行われる、ポリエステル樹脂の製造方法。
[1-8] 前記原料は、多価カルボン酸を含む、[1-7]に記載の製造方法。
[1-9] 前記エステル化工程が3時間以内である、[1-7]又は[1-8]に記載の製造方法。
[2-1] ポリエチレンテレフタレート由来の構成単位と、バイオマス由来モノマー由来の構成単位と、を含むポリエステル樹脂であって、前記バイオマス由来モノマー由来の炭素原子比率が、前記ポリエステル樹脂を構成する全炭素原子に対して30.0~90.0%であり、前記バイオマス由来モノマーは少なくともエリスリタンを含む、ポリエステル樹脂。
[2-2] エリスリタン由来の炭素原子比率が、前記ポリエステル樹脂を構成する全炭素原子に対して5.0~35.0%である、[2-1]に記載のポリエステル樹脂。
[2-3] 石油由来モノマー由来の炭素原子比率が、前記ポリエステル樹脂を構成する全炭素原子に対して30.0%以下である、[2-1]又は[2-2]に記載のポリエステル樹脂。
[2-4] 前記ポリエチレンテレフタレート由来の炭素原子比率が、前記ポリエステル樹脂を構成する全炭素原子に対して10.0~50.0%である、[2-1]~[2-3]のいずれかに記載のポリエステル樹脂。
[2-5] ガラス転移温度が30~80℃である、[2-1]~[2-4]のいずれかに記載のポリエステル樹脂。
[2-6] ポリエチレンテレフタレートと、バイオマス由来モノマーとを含む原料混合物を反応させる工程を含むポリエステル樹脂の製造方法であって、前記バイオマス由来モノマー由来の炭素原子比率が、前記原料混合物の全炭素原子に対して30.0~90.0%であり、前記バイオマス由来モノマーは少なくともエリスリタンを含む、ポリエステル樹脂の製造方法。
[2-7] エリスリタン由来の炭素原子比率が、前記原料混合物の全炭素原子に対して5.0~35.0%である、[2-6]に記載のポリエステル樹脂の製造方法。
[2-8] 石油由来モノマー由来の炭素原子比率が、前記原料混合物の全炭素原子に対して30.0%以下である、[2-6]又は[2-7]に記載のポリエステル樹脂の製造方法。
[2-9] 前記ポリエチレンテレフタレート由来の炭素原子比率が、前記原料混合物の全炭素原子に対して10.0~50.0%である、[2-6]~[2-8]のいずれかに記載のポリエステル樹脂の製造方法。
本発明の第一の態様のポリエステル樹脂は、バイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種に由来する構成単位、及びポリエチレンテレフタレート(以下、「PET」とも呼ぶ。)由来の構成単位を含み、全炭素原子100%に対して前記ポリエチレンテレフタレート由来の炭素原子比率が5~40%であり、メチルエチルケトン不溶分が5質量%以下である。
本発明の一態様のポリエステル樹脂は、PETと、バイオマス由来の多価アルコール成分及びバイオマス由来の多価カルボン酸成分のうちの少なくとも1種を含む混合物Mを原料とする。別の側面として、混合物Mは、PETと、バイオマス由来のイソソルバイド及びエリスリタンの少なくとも一種である多価アルコール成分と、バイオマス由来の多価カルボン酸成分とを含んでいてもよい。すなわち、ポリエステル樹脂は、混合物Mの反応生成物である。混合物Mに含まれるモノマーの少なくとも一部は、バイオマス由来モノマーである。混合物Mは、石油由来モノマーを含んでもよい。
「バイオマス由来モノマー」とは、植物を原料として生成されたモノマーのことをいう。バイオマス由来モノマーを構成している炭素原子は、植物に由来するものである。
「石油由来モノマー」とは、PET及びバイオマス由来モノマーを除く、石油を原料として生成されたモノマーのことをいう。石油由来モノマーを構成している炭素原子は、石油に由来するものである。
PETとしては、例えばエチレングリコールとテレフタル酸、テレフタル酸ジメチル等とのエステル化若しくはエステル交換、並びに重縮合により、常法に従って製造されたものを用いることができる。
PETとしては、未使用のPETを用いてもよいし、使用済のPET又はPET製品を再生(つまり、リサイクル)したリサイクルPETを用いてもよい。また、PETとしてバイオマス由来原料を使用したPETを用いても良いし、A-PET(非晶性ポリエチレンテレフタレート)、C-PET(結晶性ポリエチレンテレフタレート)、G-PET(グリコール変性ポリエチレンテレフタレート)を用いてもよい。
環境保全の観点から、PETとしては、リサイクルPET又はバイオマス由来原料を使用したPETが好ましい。バイオマス由来原料を使用したPETは、未使用でもよいし、使用済みでもよい。
PETは、1種を単独で用いてもよいし、2種以上を併用してもよい。
なお、混合物Mにおける全炭素原子に対するPET由来の炭素原子比率は、混合物Mを構成する各成分の炭素数およびモル比率に基づいて算出することができる。後述するイソソルバイド由来の炭素原子比率、エリスリタン由来の炭素原子比率及びバイオマス由来モノマーの炭素原子比率についても、同様に算出することができる。
PETのIV値は、フェノールと1,1,2,2-テトラクロルエタンとを質量比1:1で混合した混合溶媒30mLにPET0.3gを溶解し、得られた溶液について、ウベローデ粘度計を使用して30℃で測定した値である。
バイオマス由来の多価カルボン酸としては、2価のカルボン酸及び3価以上のカルボン酸が挙げられる。2価のカルボン酸としては、例えばテレフタル酸、イソフタル酸及びナフタレンジカルボン酸の異性体(具体的には1,4-、1,5-、1,6-、1,7-、2,5-、2,6-、2,7-、2,8-)、及びこれらの低級アルキルエステル若しくは酸無水物等の芳香族ジカルボン酸;コハク酸、イソデシルコハク酸、ドデセニルコハク酸、マレイン酸、フマル酸、アジピン酸、セバシン酸、2,5-フランジカルボン酸、及びこれらの低級アルキルエステル若しくは酸無水物等の脂肪族ジカルボン酸などが挙げられる。
テレフタル酸及びイソフタル酸の低級アルキルエステルとしては、例えばテレフタル酸ジメチル、イソフタル酸ジメチル、テレフタル酸ジエチル、イソフタル酸ジエチル、テレフタル酸ジブチル及びイソフタル酸ジブチルなどが挙げられる。
これらの中でも、2価のカルボン酸としては、ヘテロ環を含む多価カルボン酸が好ましい。また、ハンドリング性及びコストに優れる点で、テレフタル酸、イソフタル酸、アジピン酸、2,5-フランジカルボン酸及びコハク酸が好ましく、2,5-フランジカルボン酸及びコハク酸がより好ましい。
2価のカルボン酸は、1種を単独で用いてもよいし、2種以上を併用してもよい。また、後述の3価以上のカルボン酸と併用してもよい。
これらの中でも、3価以上のカルボン酸としては、ハンドリング性及びコストに優れる点で、トリメリット酸、トリメリット酸無水物、ピロメリット酸、ピロメリット酸無水物が好ましく、トリメリット酸及びその無水物が特に好ましい。
3価以上のカルボン酸は、1種を単独で用いてもよいし、2種以上を併用してもよい。
バイオマス由来の多価アルコール成分は、エチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、グリセリン、イソソルバイド、イソマンニド、エリスリタン、ソルビトール、エリスリトール等が挙げられ、ヘテロ環を含む多価アルコール成分であることが好ましい。バイオマス由来の多価アルコール成分は、イソソルバイド及びエリスリタンの少なくとも1種であることがより好ましい。
ポリエステル樹脂中のイソソルバイド由来の構成単位に含まれる炭素原子の含有量は、ポリエステル樹脂に含まれる全炭素原子に対し1~30%であることが好ましい。イソソルバイド由来の構成単位に含まれる炭素原子を1%以上用いることが環境負荷低減の面で好ましく、またポリエステル樹脂のガラス転移温度(Tgともいう)を高める効果がある。また、イソソルバイド由来の構成単位に含まれる炭素原子を30%以下とすることで、ポリエステル樹脂が着色し難くなったり、溶剤溶解性が良好となったりする傾向がある。イソソルバイド由来の構成単位に含まれる炭素原子の含有量は、5~25%がより好ましい。
他の2価のアルコールとしては、例えば、エチレングリコール、ネオペンチルグリコール、プロピレングリコール、ヘキサンジオール、ポリエチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、ジエチレングリコール、トリエチレングリコール、1,4-シクロヘキサンジメタノール、イソマンニド、及び1,4-ジヒドロキシ-2-ブテン等の脂肪族アルコール、例えば、ポリオキシプロピレン-(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン-(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン-(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン-(2.4)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシプロピレン(3.3)-2,2-ビス(4-ヒドロキシフェニル)プロパンポリオキシプロピレン(6)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン-(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン-(2.2)-2,2-ビス(4-ヒドロキシフェニル)プロパン、ポリオキシエチレン-(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン及びポリオキシプロピレン(2.2)-ポリオキシエチレン-(2.0)-2,2-ビス(4-ヒドロキシフェニル)プロパン等の芳香族アルコール、等が挙げられる。
他の2価のアルコールは、1種を単独で用いてもよいし、2種以上を併用してもよい。また、石油由来であってもバイオマス由来であっても良い。
なお、「エチレン」の後のカッコ内の数値は、エチレンオキサイドの平均付加モル数であり、「プロピレン」の後のカッコ内の数値は、プロピレンオキサイドの平均付加モル数である。
他の3価以上のアルコールは、1種を単独で用いてもよいし、2種以上を併用してもよい。また、石油由来であってもバイオマス由来であってもよい。
混合物Mは、PET、多価カルボン酸成分及び多価アルコール成分以外の成分(以下、他の成分ともいう)を含んでいてもよい。すなわち、ポリエステル樹脂は、他の成分由来の構成単位を含んでいてもよい。
他の成分としては、1価のカルボン酸、1価のアルコール及び一価のカルボン酸と一価のアルコールのモノエステルなどが挙げられる。
1価のカルボン酸としては、例えば安息香酸及びp-メチル安息香酸等の炭素数30以下の芳香族カルボン酸;ステアリン酸及びベヘン酸等の炭素数30以下の脂肪族カルボン酸;桂皮酸、オレイン酸、リノール酸及びリノレン酸等の二重結合を分子内に1つ以上有する不飽和カルボン酸などが挙げられる。
1価のアルコールとしては、例えばベンジルアルコール等の炭素数30以下の芳香族アルコール;オレイルアルコール、ラウリルアルコール、セチルアルコール、ステアリルアルコール及びベヘニルアルコール等の炭素数30以下の脂肪族アルコールなどが挙げられる。
一価のアルコールと一価のカルボン酸のモノエステルとしては、カルナバワックス、ライスワックス等の天然エステルワックスなどが挙げられる。
他の成分としては、石油由来であってもバイオマス由来であってもよいが、バイオマス由来であることがより好ましい。
本実施形態のポリエステル樹脂は、MEK不溶分が5質量%以下である。MEK不溶分は、少ない方が好ましく、最も好ましくは0質量%である。
MEK不溶分が5質量%以下であれば、溶剤系のインク、塗料等及び溶剤に溶解して使用する用途への適合性が高まる。また、水系インク及び塗料バインダー等として、ポリエステル樹脂を乳化物に加工して使用する場合を想定しても、転相乳化法等で乳化処理する際には溶剤溶解性が必須であり、5質量%以下とすることで適性が高まる。
L値は、明度を示し、黒(0)~白(100)の範囲である。数値が大きいほど明度が高いことを示す。
a値は、赤色が強いと正の値をとり、緑色が強いと負の値をとる。
本願の第一の態様のポリエステル樹脂は、褐色に着色しやすいイソソルバイドを共重合した場合でも、明度が高く、かつ赤みをおさえられている樹脂である。
均一なMEK溶液となれば、溶剤系のインク、塗料等及び溶剤に溶解して使用する用途への適合性が高まる。また、水系インク及び塗料バインダー等として、ポリエステル樹脂を乳化物に加工して使用する場合を想定しても、転相乳化法等で乳化処理する際には溶剤溶解性が必須であり、乳化適性が高まる。
均一な溶液とは、静置した際に液相の分離が見られず、沈殿物がない又はごくわずかに認められる程度の状態であることをいう。
ポリエステル樹脂のガラス転移温度は、以下のようにして求める。すなわち、示差走差熱量計(例えば、株式会社島津製作所製、「DSC60 Plus」)を用い、昇温速度5℃/分で測定したときのチャートの低温側のベースラインと、ガラス転移温度近傍にある吸熱カーブの接線との交点の温度を求め、これをガラス転移温度とする。
なお、ポリエステル樹脂の酸価が概ね6~15mgKOH/gの範囲であれば、中和転相乳化が可能となり、乳化物としての活用に適する。
ポリエステル樹脂の酸価は、ポリエステル樹脂をベンジルアルコールに溶解し、クレゾールレッドを指示薬として、0.02規定のKOH溶液を用いて滴定して求めた値である。
ポリエステル樹脂の水酸基価は、ポリエステル樹脂をテトラヒドロフランに溶解し、ジメチルアミノピリジンの存在下で無水酢酸と反応させて水酸基をアセチル化し、過剰の無水酢酸を加水分解して酢酸にした後、フェノールフタレインを指示薬として0.5規定のKOH溶液を用いて滴定し、無水酢酸の消費量から算出した値である。
次いで、フラスコカバー、撹拌翼及び冷却管を取り付け、ウォーターバス内にて70℃に加温しながらアスピレーターで減圧してMEKを留去し、水及び樹脂のみからなる乳化物を得、乳化物の粒径をレーザ回折/散乱式粒度分布測定装置(堀場製作所社製、LA-960)を用いて測定し、メジアン径(D50ともいう)を乳化物の粒径とする。
本発明の第二の態様のポリエステル樹脂の製造方法は、バイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種、及びポリエチレンテレフタレートを含む原料を、チタン化合物の存在下で反応させるエステル化反応及びエステル交換反応の少なくとも一方である反応工程と、前記反応工程で得られた反応物を重縮合する工程とを含むポリエステル樹脂の製造方法であって、前記ポリエチレンテレフタレート由来の炭素原子比率が、前記原料の全炭素原子量に対して5~40%であり、前記反応工程の少なくとも一部が、ポリエチレンテレフタレートの融点以上の温度で行われる。
以下、本発明の第二の態様のポリエステル樹脂の製造方法の一例について説明する。本実施形態のポリエステル樹脂の製造方法は、上述したバイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種、及びポリエチレンテレフタレートを含む原料であるを混合物Mを反応させる工程を含む。混合物M、即ち原料の全炭素原子量に対して、PET由来の炭素原子比率は、5~40%である。
混合物M中のPET由来の炭素原子比率は、混合物M由来の全炭素原子に対して、5~30%がより好ましい。
原料混合物M中にエリスリタンを含む場合、エリスリタン由来の炭素原子比率は、原料混合物M由来の全炭素原子に対して、5~35%が好ましく、8~28%がより好ましい。
カルボン酸チタン化合物としては、例えば蟻酸チタン、酢酸チタン、プロピオン酸チタン、オクタン酸チタン、シュウ酸チタン、コハク酸チタン、マレイン酸チタン、アジピン酸チタン、セバシン酸チタン、ヘキサントリカルボン酸チタン、イソオクタントリカルボン酸チタン、オクタンテトラカルボン酸チタン、デカンテトラカルボン酸チタン、安息香酸チタン、フタル酸チタン、テレフタル酸チタン、イソフタル酸チタン、1,3-ナフタレンジカルボン酸チタン、4,4-ビフェニルジカルボン酸チタン、2,5-トルエンジカルボン酸チタン、アントラセンジカルボン酸チタン、トリメリット酸チタン、2,4,6-ナフタレントリカルボン酸チタン、ピロメリット酸チタン及び2,3,4,6-ナフタレンテトラカルボン酸チタンなどが挙げられる。これらの中でも特に、入手しやすさ等からテトラブトキシチタンが好ましい。
上記触媒は、1種を単独で用いてもよいし、2種以上を併用してもよい。
重合終点は、例えばポリエステル樹脂の軟化温度により決定される。例えば、撹拌翼のトルクが所望の軟化温度を示す値となるまで重縮合反応を行った後、重合を終了させればよい。ここで、「重合を終了させる」とは、反応容器の攪拌を停止し、反応容器の内部に窒素を導入して容器内を常圧とすることをいう。
重縮合反応時間とは、反応系を重縮合反応温度にして減圧し始めた時点から、重合を終了させるまでの時間をいう。
冷却した後に得られたポリエステル樹脂を所望の大きさに粉砕してもよい。
以上説明した本発明の第一の態様のポリエステル樹脂は、石油由来の原料使用量の低減によって環境面及び安全面に配慮をしつつ、溶剤溶解性良好で、色味の薄いポリエステル樹脂である。そのため、淡色のインク及び塗料等の用途にも使用できる。
しかも、ポリエステル樹脂の原料の一部としてPETを用いているので、このPETが起点となり、エステル化反応やエステル交換反応が進行しやすくなるので、反応時間を短縮できる。
本実施例で示されるポリエステル樹脂の測定及び評価方法は、以下の通りである。
ポリエステル樹脂のガラス転移温度は、示差走差熱量計(株式会社島津製作所製、「DSC-60」)を用いて、昇温速度5℃/分におけるチャートのベースラインと吸熱カーブの接線との交点から測定した。測定試料は、10mg±0.5mgをアルミパン内に計量し、100℃で10分融解後、ドライアイスを用いて急冷却処理したサンプルを用いて行った。
さらに、測定結果に基づき、以下の基準で保存性を評価した。
(評価基準)
◎:Tgが50℃以上である。
○:Tgが30℃以上、50℃未満である。
×:Tgが30℃未満である。
ポリエステル樹脂の軟化温度は、フローテスター(株式会社島津製作所製、「CFT-500D」)を用いて、1mmφ×10mmのノズル、荷重294N、昇温速度3℃/分の等速昇温下で、樹脂サンプル1.0g中の1/2量が流出したときの温度を測定し、これを軟化温度とした。
ポリエステル樹脂の酸価は、以下のようにして測定した。
測定サンプル約0.2gを枝付き三角フラスコ内に精秤し(a(g))、ベンジルアルコール20mLを加え、窒素雰囲気下として230℃のヒーターにて15分加熱し測定サンプルを溶解した。室温まで放冷後、クロロホルム20mL、クレゾールレッド溶液数滴を加え、0.02規定のKOH溶液にて滴定した(滴定量=b(mL)、KOH溶液の力価=p)。ブランク測定を同様に行い(滴定量=c(mL))、以下の式に従って酸価を算出した。
酸価(mgKOH/g)={(b-c)×0.02×56.11×p}/a
ポリエステル樹脂の水酸基価は、以下のように測定した。
測定サンプル約5gを三角フラスコに精秤し(a(g))、テトラヒドロフラン50mLを加えてスターラーで撹拌溶解した。次いで、ジメチルアミノピリジン5.000gをテトラヒドロフランに溶解して500mLに調整した溶液30mLを三角フラスコに加えた。続いて、無水酢酸22mLとテトラヒドロフラン200mLとの混合液を10mL加え、15分撹拌してアセチル化した。次いで、蒸留水5mLを加えて15分撹拌し、過剰な無水酢酸を加水分解して酢酸にした。テトラヒドロフラン50mLを加えたのち、フェノールフタレイン数敵を加え、0.5規定のKOH溶液にて滴定した(滴定量=b(mL)、KOHの力価=p)。ブランク測定を同様に行い(滴定量=c(mL))、以下の式に従って水酸基価を算出した。
水酸基価(mgKOH/g)={(c-b)×0.5×56.11×p}/a+酸価
分光測色計CM-5(コニカミノルタ社製)を用い、以下の条件にてポリエステル樹脂のL値及びa値を求めた。
・使用樹脂:粒径1~2mmを篩い分けにて分取したもの
・測定条件:微小シャーレを使用した測定
測定タイプ:シャーレ測定
測定径:微小シャーレ用Φ3mm
SCI/SCE:SCE
・観察条件
表色系:ハンターLab ΔE
視野:2°
主光源:C
第2光源:なし
・測定方法
微小シャーレに樹脂を充填し、シャーレを90°ずつ回転して計4回測定を行った。測定結果を平均してL値及びa値を求めた。
ポリエステル樹脂の分子量は、GPC法によりポリスチレン換算値として以下の条件下で求めた。
装置:東ソー(株)製、HLC8020
カラム:東ソー(株)製、TSKgelGMHXL(カラムサイズ:7.8mm(ID)×30.0cm(L))を3本直列に連結
オーブン温度:40℃
溶離液:テトラヒドロフラン(THF)
試料濃度:20mg/10mL
濾過条件:0.45μmテフロン(登録商標)メンブレンフィルターで試料溶液を濾過
流速:1mL/分
注入量:0.1mL
検出器:RI
検量線作成用標準ポリスチレン試料:東ソー(株)製TSK standard、A-500(分子量5.0×102)、A-2500(分子量2.74×103)、F-2(分子量1.96×104)、F-20(分子量1.9×105)、F-40(分子量3.55×105)、F-80(分子量7.06×105)、F-128(分子量1.09×106)、F-288(分子量2.89×106)、F-700(分子量6.77×106)、F-2000(分子量2.0×107)。
<ポリエステル樹脂の製造>
酸成分100モル部に対し、PET-1を34モル部(159.2g)と、テレフタル酸60モル部(242.9g)と、無水トリメリット酸6モル部(28.1g)と、ポリオキシプロピレン-(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン65モル部(570.1g)と、イソソルバイド20モル部(71.2g)と、触媒としてテトラブトキシチタンを酸成分に対して500ppm(0.215g)とを蒸留塔備え付けの反応容器に投入した。
なお、PET-1は、テレフタル酸1モル及びエチレングリコール1モルからなるユニットをPET-1が1モルであるとし、PET-1の1モルにつき、PET由来のテレフタル酸は、酸成分1モルとして、PET由来のエチレングリコールはアルコール成分1モルとして、それぞれカウントした。
イソソルバイドは、バイオマス由来原料のものを用いた。
なお、実施例1で得られたポリエステル樹脂は、テレフタル酸由来の構成単位、無水トリメリット酸由来の構成単位、ポリオキシプロピレン-(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン由来の構成単位、イソソルバイド由来の構成単位及びエチレングリコール由来の構成単位を含み、各構成単位の割合は、仕込み組成と概ね一致する。
すなわち、実施例1で得られたポリエステル樹脂は、PET由来の炭素原子を14.1%含み、イソソルバイド由来の炭素原子を5.0%含んでいた。
<ポリエステル樹脂の製造>
表1に示す仕込み組成、エステル化反応時間及び/又はエステル交換反応時間及び重縮合反応時間に変更した以外は、実施例1と同様にしてポリエステル樹脂を製造し、各種測定及び評価を行った。なお、実施例5では、イソソルバイドに加え、バイオマス由来のコハク酸、プロピレングリコール、グリセリンを用いた。これらの結果を表1に示す。実施例6では、PET-1に変えてイソフタル酸由来の構成単位を少量含む使用済みのPETを再生した、IV値0.73のリサイクルポリエチレンテレフタレートであるPET-2を用いた。
<ポリエステル樹脂の製造>
PET-1を20モル部(100.0g)と、イソフタル酸30モル部(129.7g)と、コハク酸50モル部(153.6g)と、プロピレングリコール40モル部(79.2g)と、エリスリタン45モル部(121.9g)と、触媒としてテトラブトキシチタンを酸成分に対して500ppm(0.192g)と、を蒸留塔備え付けの反応容器に投入した。
実施例7で反応容器に投入した原料混合物Mは、酸成分が100モル部、アルコール成分が105モル部である。
モノマーのうち、コハク酸、プロピレングリコール、エリスリタンは、バイオマス由来のものを用いた。
なお、実施例7で得られたポリエステル樹脂は、テレフタル酸由来の構成単位、イソフタル酸由来の構成単位、コハク酸由来の構成単位、プロピレングリコール由来の構成単位、エリスリタン由来の構成単位及びエチレングリコール由来の構成単位を含み、各構成単位の割合は、仕込み組成と概ね一致する。
すなわち、実施例7で得られたポリエステル樹脂は、ポリエステル樹脂を構成する全炭素原子に対して、PET由来の炭素原子を21.3%、エリスリタン由来の炭素原子を19.1%、エリスリタンを含むバイオマス由来モノマー由来の炭素原子を53.2%、石油由来原料由来の炭素原子を25.5%含んでいた。
<ポリエステル樹脂の製造>
表2に示す仕込み組成、エステル化反応時間及び/又はエステル交換反応時間及び重縮合反応時間に変更した以外は、実施例7と同様にしてポリエステル樹脂を製造し、各種測定及び評価を行った。これらの結果を表2に示す。
実施例4、9及び10で得られたポリエステル樹脂について、乳化物の製造を行った。
200mlビーカーにて、ポリエステル樹脂25gをMEK75gに溶解し、ポリエステル樹脂のカルボン酸を120%中和可能な量のジメチルアミノエタノールをビーカー内に添加し十分になじませた。次いで、300ml丸底フラスコに純水100mlを投入し、そこへ上記のMEK溶液を投入してホモジナイザーにて8000rpmで10分処理した。
次いで、フラスコカバー、撹拌翼及び冷却管を取り付け、ウォーターバス内にて70℃に加温しながらアスピレーターで減圧してMEKを留去し、水及び樹脂のみからなる乳化物を得た。得られた乳化物の粒径をレーザ回折/散乱式粒度分布測定装置(堀場製作所社製、LA-960)を用いて測定し、メジアン径を乳化物の粒径とした。実施例4のポリエステル樹脂を用いた乳化物の粒径を表1に、実施例9及び10のポリエステル樹脂を用いた乳化物の粒径を表2示す。
・TPA:テレフタル酸
・IPA:イソフタル酸
・TMA:無水トリメリット酸
・Bio-ScA:バイオマス由来コハク酸
・Bio-FDCA:バイオマス由来2,5-フランジカルボン酸
・BPP:ポリオキシプロピレン-(2.3)-2,2-ビス(4-ヒドロキシフェニル)プロパン
・Bio-EG:バイオマス由来エチレングリコール
・Bio-PG:バイオマス由来プロピレングリコール(1,2-プロパンジオール):バイオマス由来
・Bio-GLY:バイオマス由来グリセリン
・Bio-イソソルバイド:バイオマス由来イソソルバイド、ロケット社製 PSAグレード
・Bio-エリスリタン:バイオマス由来エリスリタン
・PET-1:使用済みのPETを再生した、IV値0.57のリサイクルポリエチレンテレフタレート
・PET-2:イソフタル酸由来の構成単位を少量含む使用済みのPETを再生した、IV値0.73のリサイクルポリエチレンテレフタレート
なお、PETのIV値は、フェノールと1,1,2,2-テトラクロルエタンとを質量比1:1で混合した混合溶媒30mLにPET0.3gを溶解し、得られた溶液について、ウベローデ粘度計を使用して30℃で測定した。
また、転相乳化処理にて乳化物が得られることを確認した。このようなポリエステル樹脂は、水系のインク及びコーティング等での使用にも適している。
PET使用量の多い比較例2のポリエステル樹脂は、溶剤溶解性が悪化していた。
Claims (18)
- バイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種に由来する構成単位、及びポリエチレンテレフタレート由来の構成単位を含み、全炭素原子100%に対して前記ポリエチレンテレフタレート由来の炭素原子比率が5~40%であり、メチルエチルケトン不溶分が5質量%以下である、ポリエステル樹脂。
- 前記バイオマス由来の多価アルコールに由来する構成単位が、ヘテロ環を含む多価アルコールに由来する構成単位である、請求項1に記載のポリエステル樹脂。
- 前記バイオマス由来の多価アルコールがイソソルバイド及びエリスリタンの少なくとも1種である、請求項1又は2に記載のポリエステル樹脂。
- 前記バイオマス由来の多価カルボン酸に由来する構成単位が、ヘテロ環を含む多価カルボン酸に由来する構成単位である、請求項1~3のいずれか1項に記載のポリエステル樹脂。
- 前記バイオマス由来の多価カルボン酸がコハク酸及び2,5-フランジカルボン酸の少なくとも1種である、請求項1~4のいずれか1項に記載のポリエステル樹脂。
- 前記バイオマス由来の多価アルコール及び前記バイオマス由来の多価カルボン酸由来の炭素原子比率が、前記ポリエステル樹脂に含まれる全炭素原子に対し、1~95%である、請求項1~5のいずれか1項に記載のポリエステル樹脂。
- 前記バイオマス由来の多価アルコール、前記バイオマス由来の多価カルボン酸並びに前記ポリエチレンテレフタレート由来の炭素原子比率が、前記ポリエステル樹脂に含まれる全炭素原子に対し、6~100%である、請求項1~6のいずれか1項に記載のポリエステル樹脂。
- 篩い分けにて粒径1~2mmの前記ポリエステル樹脂を分取し、分光測色計にて測定した場合のL値が40以上であり、a値が2.4以下である、請求項1~7のいずれか1項に記載のポリエステル樹脂。
- 請求項1~8のいずれか1項に記載のポリエステル樹脂、及び溶剤を含む塗料。
- 請求項1~8のいずれか1項に記載のポリエステル樹脂を含むインク。
- 請求項1~8のいずれか1項に記載のポリエステル樹脂を含む粘接着材。
- 請求項1~8のいずれか1項に記載のポリエステル樹脂を含む画像形成材。
- バイオマス由来の多価アルコール及びバイオマス由来の多価カルボン酸のうちの少なくとも1種、及びポリエチレンテレフタレートを含む原料を、チタン化合物の存在下で反応させるエステル化反応及びエステル交換反応の少なくとも一方である反応工程と、前記反応工程で得られた反応物を重縮合する工程とを含むポリエステル樹脂の製造方法であって、
前記ポリエチレンテレフタレートに由来する炭素原子比率が、前記原料の全炭素原子量に対して5~40%であり、前記反応工程の少なくとも一部が、ポリエチレンテレフタレートの融点以上の温度で行われる、ポリエステル樹脂の製造方法。 - 前記バイオマス由来の多価アルコールが、ヘテロ環を含む多価アルコールである、請求項13に記載の製造方法。
- 前記バイオマス由来の多価アルコールがイソソルバイド及びエリスリタンの少なくとも1種である、請求項14に記載の製造方法。
- 前記バイオマス由来の多価カルボン酸が、ヘテロ環を含む多価カルボン酸である、請求項13に記載の製造方法。
- 前記バイオマス由来の多価カルボン酸がコハク酸及び2,5-フランジカルボン酸の少なくとも1種である、請求項16に記載の製造方法。
- 前記反応工程が3時間以内である、請求項14~17のいずれか1項に記載の製造方法。
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