WO2023013474A1 - ポリエステル樹脂組成物、水分散体、塗料組成物および塗膜 - Google Patents
ポリエステル樹脂組成物、水分散体、塗料組成物および塗膜 Download PDFInfo
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- WO2023013474A1 WO2023013474A1 PCT/JP2022/028758 JP2022028758W WO2023013474A1 WO 2023013474 A1 WO2023013474 A1 WO 2023013474A1 JP 2022028758 W JP2022028758 W JP 2022028758W WO 2023013474 A1 WO2023013474 A1 WO 2023013474A1
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- polyester resin
- resin composition
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- HOVAGTYPODGVJG-ZFYZTMLRSA-N methyl alpha-D-glucopyranoside Chemical compound CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HOVAGTYPODGVJG-ZFYZTMLRSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- UWNXTLKLPYIBSO-UHFFFAOYSA-L nickel(2+);propan-2-yloxymethanedithioate Chemical compound [Ni+2].CC(C)OC([S-])=S.CC(C)OC([S-])=S UWNXTLKLPYIBSO-UHFFFAOYSA-L 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- HVNWRBWNOPYOER-UHFFFAOYSA-N pentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)C(C(O)=O)CC(O)=O HVNWRBWNOPYOER-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- 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
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- 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
-
- 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
- C08G63/16—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
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
-
- 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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic 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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08L67/02—Polyesters derived from 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
Definitions
- the present invention relates to polyester resin compositions. More specifically, the present invention relates to a polyester resin composition suitable for can coating, and particularly to a polyester resin composition suitable for coating the inner surface of cans containing beverages and foods (hereinafter collectively referred to as food and drink). and aqueous dispersions, coating compositions, and coating films containing the same.
- Metal cans such as beverage cans and food cans are coated with an organic resin to prevent food from corroding the metal (corrosion resistance) and to preserve the flavor and flavor of the contents (flavor properties).
- These coatings are required to have workability, corrosion resistance, adhesion to metal materials, curability, and the like. Depending on the application, it may be subjected to high temperature and high humidity conditions such as retort sterilization. When applied to the outer surface side, it is also required that the coating does not whiten.
- epoxy paints such as epoxy-phenol paints, epoxy-amino paints, epoxy-acrylic paints, polyester-phenol paints, polyester - Polyester-based paints such as amino-based paints and vinyl chloride-based paints are widely used.
- bisphenol A which is a raw material of epoxy resin, may have estrogenic effects and affect the brains of fetuses and infants.
- Vinyl chloride-based paints also have the problem of stabilizers and the generation of dioxins during incineration.
- Formaldehyde which is used as a raw material for phenolic resins and amino resins and remains in paint, is known to be harmful to the human body, such as carcinogenicity, and to adversely affect the flavor of the contents.
- a resin composition for metal containers or metal lids for example, an acrylic-modified polyester resin obtained by graft-polymerizing a polymerizable unsaturated monomer component to a polyester resin having an ethylenic double bond at the end of the resin. and a ⁇ -hydroxyalkylamide crosslinking agent dispersed in an aqueous medium have been proposed (Patent Document 1).
- Patent Document 2 proposes a coating composition comprising a polyester polyol and a blocked polyisocyanate curing agent.
- the object of the present invention is that the polyester resin alone can be cured without substantially containing a curing agent, so that harmful outgas can be suppressed and a coating film having excellent properties such as adhesion, retort resistance, and workability can be formed. It is to provide a polyester resin and a polyester resin composition capable of achieving the above.
- the inventors of the present invention conducted various studies on the above, and found that a polyester resin composition containing a polyester resin having a predetermined amount of acid value and having a specific storage elastic modulus when subjected to a predetermined heat treatment substantially functions as a curing agent. It has been found that a tough coating film can be formed by using a polyester resin alone without using it as an additive. Furthermore, by specifying the resin composition and controlling the amount of catalyst, it was found that a polyester resin coating with excellent balance between adhesiveness and processability, no harmful outgassing, and markedly improved retort resistance can be obtained. , led to the present invention.
- a polyester resin composition comprising a polyester resin (A) and satisfying the following requirements (i) to (iii).
- the polyester resin (A) has an acid value of 100 eq/ton or more.
- (ii) contains substantially no curing agent;
- the polyester resin composition has a storage modulus E' of 1.0 ⁇ 10 4 Pa or more at 200° C. after heat treatment at 240° C. for 1 hour.
- polyester resin (A) As a polyol component constituting the polyester resin (A), a diol (a) having two primary hydroxyl groups and no alicyclic structure is included, and a diol (b) having an alicyclic structure and 1
- the polycarboxylic acid component constituting the polyester resin (A) contains a polycarboxylic acid having a benzene skeleton, and further includes an aliphatic polycarboxylic acid, an alicyclic polycarboxylic acid, and an aromatic polycarboxylic acid having a naphthalene skeleton.
- the polyester resin composition according to [1] above comprising at least one selected from the group consisting of: [5]
- the polyester resin (A) has a storage modulus E' at 200°C after heat treatment at 150°C for 30 minutes and is less than 1.0 ⁇ 10 4 Pa, and further contains one or more catalysts (B).
- An aqueous polyester resin dispersion comprising the polyester resin composition according to any one of [1] to [6] and an aqueous medium.
- a metal can having the coating film according to [9] above.
- An object of the present invention is to provide a polyester resin composition which does not generate harmful outgassing caused by a curing agent, has an excellent balance between curability, adhesiveness and processability, and has significantly improved retort resistance, and a coating film thereof. can be done.
- the polyester resin composition of the present invention is a polyester resin composition characterized by containing a polyester resin (A) and satisfying the following requirements (i) to (iii).
- the polyester resin (A) has an acid value of 100 eq/ton or more.
- (ii) contains substantially no curing agent;
- the polyester resin composition has a storage modulus E' of 1.0 ⁇ 10 4 Pa or more at 200° C. after heat treatment at 240° C. for 1 hour.
- the acid value of the polyester resin (A) must be 100 eq/ton or more. It is preferably 200 eq/ton or more, more preferably 250 eq/ton or more, and still more preferably 300 eq/ton or more. If it is less than the above lower limit, the curability may be lowered because there are few carboxyl groups serving as cross-linking points. Furthermore, when the acid value is less than the above lower limit, the thermal decomposition reaction proceeds predominantly over the curing reaction when heated to 240° C., and workability may deteriorate. Moreover, aqueous dispersibility becomes easy because an acid value has more than the said lower limit. Although there is no particular upper limit for the acid value, it is preferably 1200 eq/ton or less in order to reduce the amount of unreacted acid components and oligomers during the acid addition reaction.
- the acid value of the polyester resin (A) of the present invention can be given by any method.
- a method of imparting an acid value a method of addition reaction of a polycarboxylic anhydride in the late stage of polycondensation, a method of increasing the acid value in the prepolymer (oligomer) stage and then polycondensing it to obtain a polyester having an acid value
- the former method of addition reaction is preferred because of ease of operation and easy acquisition of the target acid value.
- carboxylic acid monoanhydrides include, for example, phthalic anhydride, succinic anhydride, anhydride maleic acid, trimellitic anhydride, itaconic anhydride, citraconic anhydride, 5-(2,5-dioxotetrahydrofurfuryl)-3-cyclohexene-1,2-dicarboxylic acid monoanhydride, hexahydrophthalic anhydride, Tetrahydrophthalic anhydride and the like can be mentioned, and one or more of these can be selected and used.
- trimellitic anhydride is preferred from the viewpoint of versatility and economy.
- carboxylic acid polyanhydrides include, for example, pyromellitic anhydride, 1,2,3 ,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, cyclopentanetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, ethylene glycol bistrimellitate dianhydride, 2,2′, 3,3′-diphenyltetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, ethylenetetracarboxylic dian
- a carboxylic acid monoanhydride and a carboxylic acid polyanhydride can be used alone or in combination. can also
- the polyester resin composition of the present invention contains substantially no curing agent.
- substantially free of curing agent means that the curing agent content is less than 1 part by mass (as solid content) with respect to 100 parts by mass (as solid content) of the polyester resin.
- the curing agent refers to a known curing agent that reacts with the polyester resin (A) of the present invention to form a crosslinked structure.
- Reaction, cation addition reaction, or anion addition reaction, etc. reaction to generate intermolecular carbon-carbon bonds, condensation reaction with polyvalent carboxylic acid groups and polyhydric alcohol groups in polyester resin, polyaddition reaction, Alternatively, formation of an intermolecular bond by transesterification or the like can be mentioned.
- curing agents include phenol resins, amino resins, isocyanate compounds, epoxy compounds, ⁇ -hydroxylamide compounds, unsaturated bond-containing resins, and the like.
- the content of the curing agent is less than 1 part by mass with respect to 100 parts by mass of the polyester resin (A) (solid content). More preferably less than 0.5 parts by weight, even more preferably less than 0.1 parts by weight, and most preferably no curing agent. If the content of the curing agent is higher than the above range, not only is it economically uneconomical, but also the self-condensation reaction between the curing agents reduces processability, volatilizes the blocking agent, and generates harmful outgas such as formaldehyde. Long-term storage stability may be poor.
- the polyester resin composition of the present invention is required to have a storage modulus E' of 1.0 ⁇ 10 4 Pa or more at 200° C. after heat treatment at 240° C. for 1 hour.
- a storage modulus E′ at 200° C. is 1.0 ⁇ 10 4 Pa or more, a polyester resin composition and a coating film thereof having an excellent balance between retort resistance and workability can be obtained.
- the storage modulus E′ at 200° C. is preferably 1.0 ⁇ 10 5 Pa or more, more preferably 5.0 ⁇ 10 5 Pa or more, still more preferably 1.0 ⁇ 10 6 Pa or more.
- the storage elastic modulus E' at 200°C is preferably 2.0 ⁇ 10 7 Pa or less, more preferably 8.0 ⁇ 10 6 Pa or less, and still more preferably 5.0 ⁇ 10 6 Pa or less. be. If it exceeds 2.0 ⁇ 10 7 Pa, the workability of the coating film becomes insufficient, and there is a possibility that it will not withstand the molding process into a can after coating a metal plate.
- the polyester resin composition after heat treatment of the polyester resin composition at 240° C. for 1 hour means that the polyester resin composition is coated on a copper foil so that the thickness after drying is 10 ⁇ m. , 240 ° C., after applying heat for 1 hour, the copper foil is etched using an aqueous solution of ferric chloride, and the resulting coating film is subjected to a dynamic viscoelasticity measurement device (DVA-220, IT measurement Control Co., Ltd.), the storage elastic modulus E' at 200 ° C. was calculated by measuring dynamic viscoelasticity under the conditions of a frequency of 10 Hz, a heating rate of 4 ° C./min, a distance between chucks of 15 mm, and a sample width of 4 mm. is the value of
- polyester resin (A) Next, the polyester resin (A) of the present invention will be described.
- the polyester resin (A) in the present invention is composed of a polycarboxylic acid component and a polyol component.
- the polyester resin (A) of the present invention preferably has, as a polyol component, a diol (a) having two primary hydroxyl groups and no alicyclic structure (hereinafter sometimes referred to as component (a)).
- the diol (a) having two primary hydroxyl groups and no alicyclic structure in the polyester resin (A) of the present invention is, for example, ethylene glycol, 1,3-propanediol, 2-butyl-2-ethyl-1 , 3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 2,4-diethyl-1,5-pentane Diol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4-methyl-1,7-h
- the copolymerization ratio of the diol (a) having two primary hydroxyl groups and no alicyclic structure is preferably 20 to 80 mol%, more preferably 20 to 80 mol% of the total polyol component. It is 20 to 60 mol %, more preferably 20 to 40 mol %. Within the above range, good curability and retort resistance are achieved.
- the polyester resin (A) of the present invention preferably has a diol (b) having an alicyclic structure as a polyol component.
- a diol (b) having an alicyclic structure hereinafter sometimes referred to as the (b) component
- the diol (b) having an alicyclic structure constituting the polyester resin (A) of the present invention is, for example, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane Glycols, hydrogenated bisphenols and the like can be mentioned, and one or more of these can be selected and used.
- 1,4-cyclohexanedimethanol is preferably used from the viewpoint of curability, workability and retort resistance.
- the copolymerization ratio of the diol (b) having an alicyclic structure that constitutes the polyester resin (A) of the present invention is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, in the total polyol component. It is preferably 20 to 30 mol %. Within the above range, the workability is good.
- the polyester resin (A) of the present invention comprises, as a polyol component, a diol (c) having one primary hydroxyl group and one secondary hydroxyl group and no alicyclic structure (hereinafter referred to as the (c) component). is).
- a diol (c) having one primary hydroxyl group and one secondary hydroxyl group and no alicyclic structure in the polyester resin (A) of the present invention include 1,2-propylene glycol, 1,2- Butanediol and the like can be mentioned, and one or more of these can be selected and used. Among them, it is preferable to use 1,2-propylene glycol.
- the copolymerization ratio of the diol (c) having one primary hydroxyl group and one secondary hydroxyl group and no alicyclic structure in the polyester resin (A) of the present invention is 5 to 75 mol in the total polyol component. %, more preferably 10 to 65 mol %, still more preferably 15 to 50 mol %. Within the above range, good curability and retort resistance are obtained.
- the polyester resin (A) of the present invention preferably contains either or both of the above component (a) and components (b) and (c) as polyol components.
- Component (a) is likely to form an ester bond, while component (b) and component (c) are more likely to cleave the ester bond than component (a).
- c) component promotes the rearrangement and recombination of ester bonds during heat treatment, increases the crosslink density, increases the storage elastic modulus E ', curability, retort resistance, It is presumed that a coating film having both adhesiveness and workability can be formed.
- the polycarboxylic acid component that constitutes the polyester resin (A) of the present invention is not particularly limited.
- Polycarboxylic acids having a naphthalene skeleton such as 4-naphthalene dicarboxylic acid and 1,8-naphthalene dicarboxylic acid are included. These may be used alone or in combination of two or more. Among them, it is preferable to use a polycarboxylic acid having a benzene skeleton and a polycarboxylic acid having a naphthalene skeleton in combination from the viewpoint of compatibility between workability and retort resistance.
- polycarboxylic acid having a benzene skeleton terephthalic acid is preferred, and as the polycarboxylic acid having a naphthalene skeleton, 2,6-naphthalenedicarboxylic acid is preferred.
- Examples of other polycarboxylic acid components constituting the polyester resin (A) of the present invention include aliphatic polycarboxylic acid components and alicyclic polycarboxylic acid components.
- Aliphatic polycarboxylic acid components include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and the like.
- Alicyclic polycarboxylic acid components include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid, and 1,2-cyclohexenedicarboxylic acid. One or more of these can be selected and used.
- an aliphatic polycarboxylic acid component or an alicyclic polycarboxylic acid component can improve workability.
- adipic acid and 1,4-cyclohexanedicarboxylic acid are preferred in terms of reactivity and economy.
- the copolymerization ratio thereof is preferably 5 to 40 mol % in the polycarboxylic acid component. More preferably 10 to 30 mol %. If it is out of the above range, the glass transition temperature of the polyester resin (A) may be greatly lowered and the retort resistance may be lowered.
- the polycarboxylic acid component constituting the polyester resin (A) of the present invention preferably contains an unsaturated dicarboxylic acid (d) as a structural unit.
- an unsaturated dicarboxylic acid (d) By containing the unsaturated dicarboxylic acid (d), the curability can be improved by a reaction that generates intermolecular carbon-carbon bonds due to cleavage of unsaturated bonds during heat treatment.
- the unsaturated dicarboxylic acid (d) include fumaric acid, maleic acid, itaconic acid, citraconic acid, 2,5-norbornanedicarboxylic acid, tetrahydrophthalic acid, and acid anhydrides thereof. More than one species can be used.
- the copolymerization ratio of the unsaturated dicarboxylic acid (d) is preferably 5 to 20 mol% in the polycarboxylic acid component. More preferably 10 to 15 mol %. By being within the above range, both workability and retort resistance can be achieved.
- the polyester resin (A) of the present invention preferably has a branched structure. Having a branched structure means having a branched structure in the main chain of the polyester.
- a polycarboxylic acid component and/or a polyol An example is a method of copolymerizing a tri- or more functional component as a part of the component.
- Tri- or more functional polycarboxylic acid components include, for example, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and tri- or more functional polyols include glycerin, trimethylolethane, trimethylolpropane, mannitol, sorbitol, pentaerythritol, ⁇ -methylglucoside and the like. Since the polyester resin (A) has a branched structure, the crosslink density increases when rearrangement and recombination of ester bonds occur during heat treatment, so the storage elastic modulus E 'increases, curability, retort resistance , can improve adhesion and processability.
- the copolymerization ratio of the tri- or higher functional polycarboxylic acid component is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, when the total polycarboxylic acid component is 100 mol%, More preferably, it is 1 mol % or more. Also, it is preferably 7 mol % or less, more preferably 6 mol % or less, still more preferably 5 mol % or less, and particularly preferably 4 mol % or less.
- the copolymerization ratio of the trifunctional or higher polyol component is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 1, when the total polyol component is 100 mol%. mol% or more.
- the polyester resin loses its flexibility, resulting in deterioration in processability or gelation during polymerization of the polyester.
- Raw materials derived from biomass resources can be used for the polycarboxylic acid component and the polyol component that constitute the polyester resin (A) in the present invention.
- Biomass resources are stored by converting the energy of sunlight into starch and cellulose through the photosynthesis of plants, the bodies of animals that grow by eating plants, and the bodies of plants and animals that are processed. This includes products that can be Among these, more preferable biomass resources are plant resources, such as wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, bean curd refuse, corn cob, tapioca cass, bagasse, vegetable oil cake, potato.
- buckwheat soybeans, oils and fats, used paper, papermaking residue, marine product residue, livestock excrement, sewage sludge, food waste, and the like. More preferred are corn, sugar cane, cassava and sago palm.
- the esterification/exchange temperature is preferably 180-250°C, more preferably 200-250°C.
- the reaction time is preferably 1.5 to 10 hours, more preferably 3 to 6 hours.
- the reaction time is the time from reaching the desired reaction temperature to the subsequent polycondensation reaction.
- the polyol component is distilled off from the esterified product obtained by the esterification reaction at a temperature of 220 to 280° C. under reduced pressure, and the polycondensation reaction proceeds until the desired molecular weight is reached.
- the reaction temperature for polycondensation is preferably 220 to 280°C, more preferably 240 to 275°C.
- the degree of pressure reduction is preferably 130 Pa or less. If the degree of pressure reduction is insufficient, the polycondensation time tends to become long, which is not preferable. As for the pressure reduction time from the atmospheric pressure to 130 Pa or less, it is preferable to reduce the pressure gradually over 30 to 180 minutes.
- an organic titanate compound such as tetrabutyl titanate, an organic tin compound such as germanium dioxide, antimony oxide, and tin octylate is used for polymerization.
- Organic titanic acid compounds are preferable from the viewpoint of reaction activity, and germanium dioxide is preferable from the viewpoint of resin coloring.
- the glass transition temperature of the polyester resin (A) thus obtained is preferably 40°C or higher, more preferably 60°C or higher, from the viewpoint of water resistance, particularly retort resistance of the coating film. Although there is no particular upper limit for the glass transition temperature, it is usually 130° C. or lower.
- the reduced viscosity of the polyester resin (A) of the present invention is preferably 0.2-0.6 dl/g, more preferably 0.3-0.5 dl/g. If the reduced viscosity is 0.2 dl/g or less, the curability will be insufficient, and the toughness of the coating film will be insufficient, so that there is a risk that it will not withstand molding into cans after being coated on a metal plate. On the other hand, when the reduced viscosity is 0.6 dl/g or more, the melt viscosity and the solution viscosity become high, and not only workability is lowered, but also the number of terminal hydroxyl groups is reduced, so there is a risk that a sufficient acid value cannot be imparted. .
- the polyester resin (A) of the present invention preferably has a storage modulus E′ of less than 1.0 ⁇ 10 4 Pa at 200° C. after heat treatment at 150° C. for 30 minutes. It is more preferably less than 1.0 ⁇ 10 3 Pa, still more preferably less than 1.0 ⁇ 10 2 Pa, and may be less than 1.0 ⁇ 10 1 Pa. Under relatively low temperature heating conditions of about 150 ° C., the storage elastic modulus E' at 200 ° C. is less than the above value, so that the generation of aggregates when dissolved in a solvent or when made into an aqueous dispersion is suppressed. can do.
- the polyester resin composition of the present invention preferably further contains a catalyst (B).
- a catalyst (B) By containing the catalyst (B), the self-crosslinking property of the polyester resin (A) during heat treatment can be promoted, the storage elastic modulus E′ can be increased, and the performance of the cured film can be improved.
- the catalyst examples include acid catalysts such as sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, camphorsulfonic acid, and phosphoric acid, and amine blocks ( partially neutralized with amine), organic tin compounds such as dibutyltin dilaurate, titanium compounds such as titanium tetrabutoxide, zinc compounds such as zinc acetate, hafnium compounds such as hafnium chloride/THF complex, scandium triflate, etc. Examples include rare earth compounds, and one or more of these can be used in combination. Of these, dodecylbenzenesulfonic acid and neutralized products thereof are preferred from the viewpoint of compatibility with the polyester resin (A) and sanitation.
- acid catalysts such as sulfuric acid, p-toluenesulf
- the catalyst (B) may be contained in the polyester resin (A) or may be added later. From the viewpoint of avoiding gelation during polymerization of the polyester resin (A), it is preferable to add the catalyst (B) after the production of the polyester resin (A).
- a radical polymerization inhibitor (C) may be added to the polyester resin composition of the present invention. It is mainly used to prevent gelation due to cleavage of unsaturated bonds when the polyester resin (A) is polymerized, but it may be added after the polymerization in order to improve the storage stability of the polyester resin.
- the radical polymerization inhibitor (C) include known antioxidants such as phenol antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants and inorganic compound antioxidants.
- Phenolic antioxidants include 2,5-di-t-butylhydroquinone, 4,4′-butyldenbis(3-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4 -hydroxy-5-t-butylphenyl)butane, 1,3,5-tris-methyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3 ,5-di-t-butyl-4-hydroxyphenyl)isocyanurate and derivatives thereof.
- Phosphorus antioxidants include tri(nonylphenyl)phosphite, triphenylphosphite, diphenylisodecylphosphite, trioctadecylphosphite, tridecylphosphite, diphenyldecylphosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl ditridecylphosphite), distearyl-pentaerythritol diphosphite, trilauryltrithiophosphite, and derivatives thereof.
- Amine antioxidants include phenyl-beta-naphthylamine, phenothiazine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-betanaphthyl-p-phenylenediamine, N-cyclohexyl-N'- Phenyl-p-phenylenediamine, aldol-alpha-naphthylamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymers, and derivatives thereof.
- sulfur-based antioxidants include thiobis(N-phenyl-beta-naphthylamine, 2-mercaptobenchiazole, 2-mercaptobenzimidazole, tetramethylthiuram disulfide, nickel isopropylxanthate, and derivatives thereof.
- Nitro compound antioxidants include 1,3,5-trinitrobenzene, p-nitrosodiphenylamine, p-nitrosodimethylaniline, 1-chloro-3-nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, Nitrobenzene, p-nitrobenzoic acid, nitrobenzene, 2-nitro-5-cyanothiophene, etc., or derivatives thereof.
- inorganic compound antioxidants include FeCl 3 , Fe(CN) 3 , CuCl 2 , CoCl 3 , Co(ClO 4 ) 3 , Co(NO 3 ) 3 , Co 2 (SO 4 ) 3 and the like.
- radical polymerization inhibitor (C) used in the present invention among the above antioxidants, phenolic antioxidants and amine antioxidants are preferable from the viewpoint of thermal stability, and have a melting point of 120 ° C. or higher and a molecular weight more preferably 200 or higher, and more preferably 170° C. or higher. Specific examples include phenothiazine and 4,4'-butyldenbis(3-methyl-6-t-butylphenol).
- polyester resin composition of the present invention known inorganic pigments such as titanium oxide and silica, phosphoric acid and its esters, surface smoothing agents, antifoaming agents, dispersants, lubricants and the like are added according to the required properties. of additives can be blended.
- lubricants are important for imparting lubricity to coating films required during the molding of DI cans and DR (or DRD) cans.
- suitable lubricants include silicone waxes, fluorine waxes, polyolefin waxes such as polyethylene, lanolin waxes, montan waxes, and microcrystalline waxes. Lubricants can be used singly or in combination of two or more.
- the polyester resin composition of the present invention can be dissolved in a known organic solvent and made into a paint.
- organic solvents used for coating include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, methyl cellosolve, butyl cellosolve, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene Glycol monoacetate, methanol, ethanol, butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, Solvesso and the like. From these, one or two or more are selected and used in consideration of solubility, evaporation rate, and the like.
- the polyester resin composition of the present invention can be made into a powder coating by a known pulverization method.
- known pulverization methods include pulverization methods.
- the polyester resin composition of the present invention and, if necessary, a mixture of antirust pigments and additives are dry-mixed in a mixer such as a tumbler mixer or a Henschel mixer, and melt-kneaded in a kneader.
- a mixer such as a tumbler mixer or a Henschel mixer
- melt-kneaded in a kneader melt-kneaded in a kneader.
- a general kneader such as a single-screw or twin-screw extruder, a triple roll, or a lab blast mill can be used.
- Pulverizers include, for example, a jet pulverizer that pulverizes using a supersonic jet stream, and a space formed between a rotor and a liner that rotate at high speed.
- An impact pulverizer that pulverizes by introducing is mentioned.
- additives may be added to the pulverized product.
- a powder coating composition can be obtained by classifying the pulverized material to adjust the powder to a desired particle size and particle size distribution.
- a known classifier capable of removing excessively pulverized toner base particles by classification by centrifugal force and wind power can be used, for example, a swirling wind classifier (rotary wind classifier) can be used.
- the polyester resin composition of the present invention can be blended with other resins for the purpose of improving the flexibility and adhesion of the coating film.
- other resins include amorphous polyesters, crystalline polyesters, ethylene-polymerizable unsaturated carboxylic acid copolymers, and ethylene-polymerizable carboxylic acid copolymer ionomers, and are selected from these. Blending at least one or more resins may sometimes impart flexibility and/or adhesion to the coating film.
- the polyester resin composition of the present invention is a metal plate made of a metal material that can be used for beverage cans, cans for cans, lids, caps, etc., it can be applied to one or both sides of the metal plate, and if necessary, to the end face. Can be painted.
- the metal material include tinplate, tin free steel, and aluminum.
- the metal plates made of these metal materials are subjected to phosphate treatment, chromic acid chromate treatment, phosphoric acid chromate treatment, anti-corrosion treatment with other anti-corrosion agents, and surface treatment for the purpose of improving the adhesion of the coating film. You can use things.
- the polyester resin composition of the present invention can be applied to a metal plate and cured by a known coating method such as roll coater coating or spray coating.
- the coating film thickness is not particularly limited, but the dry film thickness is preferably in the range of 3 to 18 ⁇ m, more preferably 5 to 15 ⁇ m.
- the baking conditions for the coating film are usually about 180 to 260° C. for about 10 minutes to 2 hours, preferably about 200 to 240° C. for about 5 minutes to 1 hour.
- the polyester resin composition of the present invention can also be dispersed in an aqueous medium and used as an aqueous polyester resin dispersion.
- a method for forming a water dispersion of the polyester resin (A) of the present invention the polyester resin (A) is dissolved in a water-soluble organic solvent in which the polyester resin (A) dissolves, and if necessary, a basic compound and water are added.
- a method (a) of sequentially adding and dispersing, a method (b) of adding a polyester resin (A) and water, a water-soluble organic solvent that dissolves the polyester resin (A), and, if necessary, a basic compound, followed by heating and dispersing, and the like. be.
- the former method (a) is preferred from the viewpoint of film-forming properties.
- the temperature for dissolving the polyester resin (A) is preferably 40 to 160°C, more preferably 50 to 140°C, still more preferably 60 to 120°C, and most preferably 70 to 100°C. If the temperature is less than 40°C, the polyester resin (A) may not be sufficiently dissolved, and the entanglement of the molecular chains cannot be sufficiently released. If the temperature exceeds 160°C, the polyester resin (A) deteriorates. This is because the risk of inviting Organic solvents in which the polyester resin (A) can be dissolved by heating in the temperature range of 40 to 160° C.
- methyl ethyl ketone dimethylacetamide, dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,3 -dioxane, 1,3-dioxolane, 1,2-hexanediol, methyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, triethylene glycol monobutyl ether and the like.
- methyl ethyl ketone, butyl cellosolve, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like are preferred.
- the temperature of the polyester resin solution is cooled to 100° C. or lower, and water and, if necessary, a basic compound are successively added while stirring the resin solution. It is necessary to obtain an aqueous dispersion by performing a phase inversion.
- a compound that volatilizes during the drying or baking process during coating film formation is preferable, such as ammonia and/or a compound having a boiling point of 250° C. or less.
- An organic amine compound or the like is used.
- These basic compounds are required in an amount capable of at least partially neutralizing the carboxyl groups of the polyester resin (A), and specifically, 0.5 to 1.5 equivalents are added to the carboxyl group equivalents. is desirable.
- the average particle size of the polyester resin water dispersion according to the present invention is very important because it greatly affects the coating film appearance and storage stability, and is preferably 30 to 250 nm. More preferably 50 to 200 nm, particularly preferably 70 to 150 nm.
- the average particle size exceeds 250 nm, not only is the dispersion stability significantly lowered, but also the film-forming properties are lowered, resulting in poor appearance of the resulting film.
- it is less than 30 nm the film-forming property tends to be remarkably improved, but this tends to cause coalescence and aggregation between the dispersed particles, resulting in a high possibility of causing thickening and poor dispersion, which is preferable. do not have.
- the polyester resin aqueous dispersion of the present invention is preferably produced with a resin solid content concentration of 10 to 45% by mass. It is more preferably 15 to 40% by mass, and still more preferably 20 to 35% by mass. If the resin solid content concentration exceeds 45% by mass, the viscosity of the aqueous dispersion increases, and aggregation between resin particles tends to occur, resulting in a significant decrease in dispersion stability. On the other hand, if it is less than 10% by mass, it is difficult to say that it is practical from both the manufacturing and usage standpoints.
- the polyester resin aqueous dispersion of the present invention is ideal for the inner surface coating of food and beverage cans.
- Various additives may be blended depending on the purpose for the inner surface coating of cans for food and beverages. Coatability, smoothness of the coating film, leveling agents and surfactants for improving the appearance, lubricants for preventing scratches on the coating film, further coloring pigments and in some cases polyester resins other than the polyester resin of the present invention, Resins other than polyester resins, such as acrylic resin emulsions and polyurethane resin emulsions, can be blended to the extent that the objects of the present invention, such as food sanitation and flavor properties, are not impaired.
- a paint using the polyester resin aqueous dispersion of the present invention can be applied to a metal substrate for cans such as aluminum, stainless steel, and tinplate by a gravure roll coater, a comma coater, a spray method, or the like.
- the film thickness is not particularly limited, but the dry film thickness is usually in the range of 3 to 18 ⁇ m, preferably 5 to 15 ⁇ m.
- the baking conditions for the coating film are usually about 180 to 260° C. for about 10 minutes to 2 hours, preferably about 200 to 240° C. for about 5 minutes to 1 hour.
- ⁇ Polyester resin (A)> (1) Measurement of Resin Composition A sample of polyester resin (A) was dissolved in deuterated chloroform and subjected to 1H-NMR analysis using a nuclear magnetic resonance (NMR) device 400-MR manufactured by VARIAN. A molar ratio was obtained from the integral value ratio.
- NMR nuclear magnetic resonance
- Tg glass transition temperature
- the storage elastic modulus E' at 200°C after heat treatment at 240°C for 1 hour was measured by coating a polyester resin composition on a copper foil so that the thickness after drying was 10 ⁇ m, After applying heat at 240 ° C for 1 hour, the copper foil is etched using an aqueous solution of ferric chloride, and the resulting coating film is subjected to a dynamic viscoelasticity measurement device (DVA-220, IT measurement control Co., Ltd.), the dynamic viscoelasticity was measured under the conditions of a frequency of 10 Hz, a heating rate of 4° C./min, a distance between chucks of 15 mm, and a sample width of 4 mm, and the storage elastic modulus E′ at 200° C.
- DVA-220 dynamic viscoelasticity measurement device
- the storage elastic modulus E′ at 200° C. after heat treatment at 150° C. for 30 minutes was determined in the same manner as above except that the heat treatment was performed at 150° C. for 30 minutes.
- the storage elastic modulus E′ was less than 1.0 ⁇ 10 4 Pa, the coating film was broken during the measurement, and the value could not be calculated.
- test piece A polyester resin composition was coated on one side of a tin plate (JIS G 3303 (2008) SPTE, 70 mm ⁇ 150 mm ⁇ 0.3 mm) with a bar coater so that the film thickness after drying was 10 ⁇ 2 ⁇ m, and baking conditions were 240. C. (PMT: highest temperature reached to the base material) ⁇ 1 hour, and hardened and baked to obtain a test piece (hereinafter referred to as a test piece).
- PMT highest temperature reached to the base material
- the obtained test piece was bent 180° in the direction in which the cured film was on the outside, and cracking of the cured film occurring at the bent portion was evaluated by measuring the current value.
- the bending process was performed without inserting anything (so-called 0T).
- a sponge width 20 mm, depth 50 mm, thickness 10 mm
- a 1% NaCl aqueous solution was placed on an aluminum plate electrode (width 20 mm, depth 50 mm, thickness 0.5 mm). The vicinity of the central portion of the bent portion of the test piece was brought into contact with the sponge so as to be parallel to the 20 mm side.
- a DC voltage of 5.0 V was applied between the aluminum plate electrode and the non-coated portion on the back surface of the test plate, and the energization value was measured.
- a smaller energization value means better bending characteristics. (judgement) ⁇ : Less than 0.5 mA ⁇ : 0.5 mA or more and less than 1.0 mA ⁇ : 1.0 mA or more and less than 2.0 mA ⁇ : 2.0 mA or more
- Curability Evaluation Gauze felt impregnated with methyl ethyl ketone was pressed against the cured film surface of the test piece so as to contact 1 cm 2 , and a rubbing test was performed by applying a load of 500 g. The number of times until the cured film was peeled off (once per reciprocation) was evaluated according to the following criteria.
- TBT tetra-n-butyl titanate
- polyester resin of the present invention (synthesis example (a)).
- the obtained polyester resin had a reduced viscosity of 0.33 dl/g, a glass transition temperature (Tg) of 65° C., and an acid value of 300 eq/ton.
- Synthesis examples (b) to (s) The polyester resins of the present invention (synthesis examples (b) to (s)) having resin compositions shown in Table 1 were produced by the direct polymerization method in the same manner as in synthesis example (a), except that the charging composition was changed. bottom.
- a polyester resin composition was prepared using the obtained polyester resin and evaluated for processability, curability, adhesion and retort resistance.
- Tables 2 and 3 show the formulation of the polyester resin composition and the evaluation results.
- the cured film (coating film) obtained from the polyester resin composition using the polyester resin (A) of the present invention has any of its workability, curability, adhesiveness, and retort resistance. is also excellent.
- the present invention relates to a polyester resin composition and a polyester resin aqueous dispersion which are excellent in workability, curability, adhesiveness and retort resistance, and a coating material and a coating film containing the same, and metal cans for food and beverages. It is suitable as a main agent for paints that are applied to other surfaces.
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Abstract
Description
[1] ポリエステル樹脂(A)を含み、次の(i)~(iii)の要件を満たすことを特徴とするポリエステル樹脂組成物。
(i)ポリエステル樹脂(A)の酸価が100eq/ton以上である。
(ii)硬化剤を実質的に含有しない。
(iii)ポリエステル樹脂組成物を240℃で1時間加熱処理後の200℃における貯蔵弾性率E’が1.0×104Pa以上である。
[2] ポリエステル樹脂(A)が分岐構造を有する、前記[1]に記載のポリエステル樹脂組成物。
[3] ポリエステル樹脂(A)を構成するポリオール成分として、1級水酸基を2個有し脂環構造を有さないジオール(a)を含み、さらに、脂環構造を有するジオール(b)および1個の1級水酸基と1個の2級水酸基を有し脂環構造を有さないジオール(c)のいずれかまたは両方を含む、前記[1]に記載のポリエステル樹脂組成物。
[4] ポリエステル樹脂(A)を構成するポリカルボン酸成分として、ベンゼン骨格を有するポリカルボン酸を含み、さらに脂肪族ポリカルボン酸、脂環族ポリカルボン酸、ナフタレン骨格を有する芳香族ポリカルボン酸からなる群より選ばれる少なくとも一種を含む、前記[1]に記載のポリエステル樹脂組成物。
[5] ポリエステル樹脂(A)を構成するポリカルボン酸成分として、不飽和ジカルボン酸(d)を含む、前記[1]に記載のポリエステル樹脂組成物。
[6] 前記ポリエステル樹脂(A)の150℃で30分加熱処理後の200℃における貯蔵弾性率E’が1.0×104Pa未満であり、さらに触媒(B)を1種以上含む、前記[1]に記載のポリエステル樹脂組成物。
[7] 前記[1]~[6]のいずれかに記載のポリエステル樹脂組成物と、水性媒体とを含むポリエステル樹脂水分散体。
[8] 前記[1]~[6]のいずれかに記載のポリエステル樹脂組成物または前記[7]に記載のポリエステル樹脂水分散体のいずれかを含有する塗料組成物。
[9] 前記[1]~[6]のいずれかに記載のポリエステル樹脂組成物を含有する塗膜。
[10] 前記[9]に記載の塗膜を有する金属缶。
(i)ポリエステル樹脂(A)の酸価が100eq/ton以上である。
(ii)硬化剤を実質的に含有しない。
(iii)ポリエステル樹脂組成物を240℃で1時間加熱処理後の200℃における貯蔵弾性率E’が1.0×104Pa以上である。
要件(i)について説明する。ポリエステル樹脂(A)の酸価は100eq/ton以上であることが必要である。好ましくは200eq/ton以上であり、より好ましくは250eq/ton以上であり、さらに好ましくは300eq/ton以上である。上記下限値未満であると、架橋点となるカルボキシル基が少ないため、硬化性が低下することがある。さらに、酸価が上記下限値未満であると、240℃に加熱した際に硬化反応より熱分解反応が優位に進行し、加工性が低下する場合がある。また、酸価が上記下限値以上を有することで、水性分散化が容易となる。酸価の上限値は特にないが、酸付加反応時の酸成分の未反応物やオリゴマー量を少なくするためには、1200eq/ton以下が好ましい。
要件(ii)について説明する。本発明のポリエステル樹脂組成物は実質的に硬化剤を含有しない。この「実質的に硬化剤を含有しない」とは、「ポリエステル樹脂100質量部(固形分換算)に対し、硬化剤含有量が1質量部未満(固形分換算)であること」を意味する。
ここで硬化剤とは、本発明のポリエステル樹脂(A)と反応し架橋構造を形成する既知の硬化剤を指し、架橋構造の形態は、例えば、ポリエステル樹脂中の不飽和二重結合をラジカル付加反応、カチオン付加反応、またはアニオン付加反応等によって反応させ、分子間炭素-炭素結合を生成させる反応や、ポリエステル樹脂中の多価カルボン酸基、多価アルコール基との縮合反応、重付加反応、またはエステル交換反応等による分子間結合の形成等が挙げられる。硬化剤としては、例えば、フェノール樹脂、アミノ樹脂、イソシアネート化合物、エポキシ化合物、またはβ-ヒドロキシルアミド化合物、不飽和結合含有樹脂などを挙げることができる。
要件(iii)について説明する。本発明のポリエステル樹脂組成物は、240℃で1時間加熱処理後の200℃における貯蔵弾性率E’が1.0×104Pa以上であることが必要である。200℃における貯蔵弾性率E’が1.0×104Pa以上であることで、耐レトルト性と加工性のバランスに優れたポリエステル樹脂組成物およびその塗膜が得られる。200℃における貯蔵弾性率E’は好ましくは1.0×105Pa以上であり、より好ましくは5.0×105Pa以上であり、さらに好ましくは1.0×106Pa以上である。1.0×104Pa未満では硬化性が不十分となり、塗膜の強靭性が不足して、耐レトルト性や接着性の低下や金属板にコーティングした後の缶への成型加工に耐えない恐れがある。
また、200℃における貯蔵弾性率E’は好ましくは2.0×107Pa以下であり、より好ましくは8.0×106Pa以下であり、さらに好ましくは5.0×106Pa以下である。
2.0×107Paを超えると、塗膜の加工性が不足して、金属板にコーティングした後の缶への成型加工に耐えない恐れがある。
ここで、「ポリエステル樹脂組成物を240℃で1時間加熱処理後の200℃における貯蔵弾性率E’」とは、銅箔上にポリエステル樹脂組成物を乾燥後の厚みが10μmとなるよう塗布し、240℃、1時間で熱を加えた後、塩化第二鉄水溶液を用いて銅箔のエッチング処理を行い、得られた塗膜に対し動的粘弾性測定装置(DVA-220、アイティー計測制御株式会社製)を用いて、周波数10Hz、昇温速度4℃/min、チャック間距離15mm、サンプル幅4mmの条件で動的粘弾性を測定して算出した、200℃における貯蔵弾性率E’の値である。
次に、本発明のポリエステル樹脂(A)について説明する。
本発明におけるポリエステル樹脂(A)は、ポリカルボン酸成分とポリオール成分から構成されるものである。
本発明のポリエステル樹脂組成物には、さらに触媒(B)を含有することが好ましい。触媒(B)を含有することで、ポリエステル樹脂(A)の加熱処理時の自己架橋性を促進し、貯蔵弾性率E’が上昇し、硬化膜の性能を向上させることができる。触媒としては、例えば硫酸、p-トルエンスルホン酸、ドデシルベンゼンスルホン酸、ナフタレンスルホン酸、ジノニルナフタレンスルホン酸、ジノニルナフタレンジスルホン酸、樟脳スルホン酸、リン酸等の酸触媒及びこれらをアミンブロック(アミンを添加し一部中和)したもの、ジブチル錫ジラウリレート等の有機スズ化合物、チタンテトラブトキシド等のチタン化合物、酢酸亜鉛などの亜鉛化合物、塩化ハフニウム・THF錯体などのハフニウム化合物、スカンジウムトリフラートなどの希土類化合物が挙げられ、これらの中から1種、又は2種以上を併用することができる。中でもポリエステル樹脂(A)との相容性、衛生性の面からドデシルベンゼンスルホン酸、及びこの中和物が好ましい。
本発明のポリエステル樹脂組成物は、水性媒体中に分散させ、ポリエステル樹脂水分散体として使用することもできる。
本発明のポリエステル樹脂(A)を水分散体化する方法としては、ポリエステル樹脂(A)をポリエステル樹脂(A)が溶解する水溶性有機溶剤に溶解し、必要に応じて塩基性化合物、水を逐次加え分散する方法(a)、ポリエステル樹脂(A)と水、ポリエステル樹脂(A)を溶解する水溶性有機溶剤、必要に応じて塩基性化合物を加え、加熱し分散する方法(b)等がある。また、有機溶剤を減量したい場合、あるいは完全に除去して水分散体化したい場合は100℃以下の沸点を有する有機溶剤を用いて分散した後、加熱、もしくは減圧下で溶剤を抜き取ることも可能である。本発明のポリエステル樹脂(A)の場合は、造膜性の点から前者の方法(a)で行うことが好ましい。
(1)樹脂組成の測定
ポリエステル樹脂(A)の試料を、重クロロホルムに溶解し、VARIAN社製 核磁気共鳴(NMR)装置400-MRを用いて、1H-NMR分析を行った。その積分値比より、モル比を求めた。
ポリエステル樹脂(A)の試料0.1gをフェノール/テトラクロロエタン(質量比6/4)の混合溶媒25ccに溶解し、30℃で測定した。
示差走査型熱量計(SII社、DSC-200)により測定した。ポリエステル樹脂(A)の試料5mgをアルミニウム製の抑え蓋型容器に入れて密封し、液体窒素を用いて-50℃まで冷却し、次いで150℃まで20℃/分にて昇温させた。この過程にて得られる吸熱曲線において、吸熱ピークが出る前のベースラインと、吸熱ピークに向かう接線との交点の温度をもって、ガラス転移温度(Tg、単位:℃)とした。
ポリエステル樹脂(A)の試料0.2gを40mlのクロロホルムに溶解し、0.01Nの水酸化カリウムエタノール溶液で滴定し、ポリエステル樹脂106gあたりの当量(eq/ton)を求めた。指示薬にはフェノールフタレインを用いた。
ポリエステル樹脂(A)100重量部(固形分)をシクロヘキサノン/ソルベッソ-150=1/1(重量比)で塗装に適した粘度になるように溶解した。表2および表3の配合に従い、ポリエステル樹脂組成物(固形分約35質量%)を得た。
240℃で1時間加熱処理後の200℃における貯蔵弾性率E’は、銅箔上にポリエステル樹脂組成物を乾燥後の厚みが10μmとなるよう塗布し、240℃、1時間で熱を加えた後、塩化第二鉄水溶液を用いて銅箔のエッチング処理を行い、得られた塗膜に対し動的粘弾性測定装置(DVA-220、アイティー計測制御株式会社製)を用いて、周波数10Hz、昇温速度4℃/min、チャック間距離15mm、サンプル幅4mmの条件で動的粘弾性を測定し、200℃における貯蔵弾性率E’を算出した。
また、150℃で30分加熱処理後の200℃における貯蔵弾性率E’は、加熱処理の条件を150℃とし、30分加熱した以外は上記と同様にして求めた。
なお、貯蔵弾性率E’が1.0×104Paを下回ったときは、塗膜が測定中に破断してしまい、値を算出できなかった。
ブリキ板(JIS G 3303(2008) SPTE、70mm×150mm×0.3mm)の片面にバーコーターで、ポリエステル樹脂組成物を乾燥後の膜厚が10±2μmになるように塗装し、焼付条件240℃(PMT:基材到達最高温度)×1時間として硬化焼き付けを行い、これを試験片とした(以下、試験片という)。
得られた試験片を、硬化膜が外側となる方向に180°折り曲げ加工を施し、折り曲げ部に発生する硬化膜の割れについて、通電値を測定することにより評価した。なお、折り曲げ加工は、間に何も挟み込まず(いわゆる0T)に折り曲げた。アルミ板製の電極(幅20mm、奥行き50mm、厚さ0.5mm)の上に1%NaCl水溶液に浸したスポンジ(幅20mm、奥行き50mm、厚さ10mm)を載せたものを用意し、スポンジの20mmの辺と平行になるように試験片の折り曲げ部の中央部付近をスポンジに接触させた。アルミ板電極と試験板の裏面の非塗装部との間に5.0Vの直流電圧をかけ、通電値を測定した。通電値が小さい方が折り曲げ特性が良好であることを意味する。
(判定)
◎:0.5mA未満
○:0.5mA以上1.0mA未満
△:1.0mA以上2.0mA未満
×:2.0mA以上
試験片の硬化膜面に、メチルエチルケトンを浸したガーゼフェルトを1cm2接触するように押し当て、500gの荷重をかけてラビング試験を行った。硬化膜が剥がれるまでの回数(一往復で一回とする)を、以下の基準で評価した。
(判定)
◎:50回以上でも塗膜が剥がれず、硬化膜に変化がみられなかった
○:25~49回で硬化膜が剥がれ、ブリキ板が露出した
△:16~24回で硬化膜が剥がれ、ブリキ板が露出した
×:15回以下で硬化膜が剥がれ、ブリキ板が露出した
試験片の硬化膜面に、カッターナイフにて1mm間隔で100個の碁盤目を作り、その上にセロハン粘着テープを密着させて60°の角度で引き剥がした。剥離が生じなかった割合で金属密着性を評価した。全く剥離が生じなかった場合は100%、全て剥がれた場合は0%である。
(判定)
◎:100% (剥離なし)
○:75%以上100%未満
△:30%以上75%未満
×:30%未満
試験片を立ててステンレスカップに入れ、これにイオン交換水を試験片の半分の高さになるまで注ぎ、これをレトルト試験機(トミー工業(株)製 ES-315)の圧力釜の中に設置し、125℃×30分のレトルト処理を行なった。処理後の評価は、一般的に硬化膜に対してより厳しい条件にさらされることになると思われる蒸気接触部分で行い、硬化膜の白化、ブリスターの状態を目視で以下のように判定した。
(判定)
◎:良好(白化、ブリスターともになし)
○:わずかに白化はあるがブリスターはない
△:若干の白化および/または若干のブリスターがある
×:著しい白化および/または著しいブリスターがある
テレフタル酸ジメチル670質量部、2,6-ナフタレンジカルボン酸ジメチル100重量部、フマル酸50質量部、無水トリメリット酸8質量部、エチレングリコール190質量部、1,2-プロパンジオール330質量部、1,4-シクロヘキサンジメタノール190質量部、触媒としてテトラ-n-ブチルチタネート(以下、TBTと略記する場合がある)0.4質量部(全酸成分に対して0.03モル%)を3L四つ口フラスコに仕込み、3時間かけて230℃まで徐々に昇温しながら、エステル化反応を行った。次いで、系内を徐々に減圧していき、1時間かけて10mmHgまで減圧重合を行うとともに温度を250℃まで昇温し、さらに1mmHg以下の真空下で50分間後期重合を行なった。目標分子量に達したらこれを窒素雰囲気下で210℃に冷却した。次いで無水トリメリット酸26質量部を投入し、窒素雰囲気下、200~230℃、30分攪拌を継続した。これを取り出し、本発明のポリエステル樹脂(合成例(a))を得た。得られたポリエステル樹脂の還元粘度は0.33dl/g、ガラス転移温度(Tg)は65℃、酸価は300eq/tonであった。
合成例(a)と同様に直接重合法にて、但し仕込み組成を変更して、樹脂組成が表1に示されるような本発明のポリエステル樹脂(合成例(b)~(s))を製造した。
Claims (10)
- ポリエステル樹脂(A)を含み、次の(i)~(iii)の要件を満たすことを特徴とするポリエステル樹脂組成物。
(i)ポリエステル樹脂(A)の酸価が100eq/ton以上である。
(ii)硬化剤を実質的に含有しない。
(iii)ポリエステル樹脂組成物を240℃で1時間加熱処理後の200℃における貯蔵弾性率E’が1.0×104Pa以上である。 - ポリエステル樹脂(A)が分岐構造を有する、請求項1に記載のポリエステル樹脂組成物。
- ポリエステル樹脂(A)を構成するポリオール成分として、1級水酸基を2個有し脂環構造を有さないジオール(a)を含み、さらに、脂環構造を有するジオール(b)および1個の1級水酸基と1個の2級水酸基を有し脂環構造を有さないジオール(c)のいずれかまたは両方を含む、請求項1に記載のポリエステル樹脂組成物。
- ポリエステル樹脂(A)を構成するポリカルボン酸成分として、ベンゼン骨格を有するポリカルボン酸を含み、さらに脂肪族ポリカルボン酸、脂環族ポリカルボン酸、ナフタレン骨格を有するポリカルボン酸からなる群より選ばれる少なくとも一種を含む、請求項1に記載のポリエステル樹脂組成物。
- ポリエステル樹脂(A)を構成するポリカルボン酸成分として不飽和ジカルボン酸(d)を含む、請求項1に記載のポリエステル樹脂組成物。
- 150℃で30分加熱処理後の200℃における貯蔵弾性率E’が1.0×104Pa未満であり、さらに触媒(B)を1種以上含む、請求項1に記載のポリエステル樹脂組成物。
- 請求項1~6のいずれかに記載のポリエステル樹脂組成物と、水性媒体とを含むポリエステル樹脂水分散体。
- 請求項1~6のいずれかに記載のポリエステル樹脂組成物または請求項7に記載のポリエステル樹脂水分散体のいずれかを含有する塗料組成物。
- 請求項1~6のいずれかに記載のポリエステル樹脂組成物を含有する塗膜。
- 請求項9に記載の塗膜を有する金属缶。
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PCT/JP2022/028758 WO2023013474A1 (ja) | 2021-08-02 | 2022-07-26 | ポリエステル樹脂組成物、水分散体、塗料組成物および塗膜 |
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EP (1) | EP4382569A1 (ja) |
JP (1) | JPWO2023013474A1 (ja) |
KR (1) | KR20240038090A (ja) |
CN (1) | CN117751161A (ja) |
TW (1) | TW202309134A (ja) |
WO (1) | WO2023013474A1 (ja) |
Citations (10)
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JP2001081160A (ja) | 1999-09-13 | 2001-03-27 | Unitika Ltd | 金属缶内面用の被膜形成用共重合ポリエステル樹脂、並びにこれを含有する塗料 |
JP2003089746A (ja) * | 2001-07-06 | 2003-03-28 | Toyobo Co Ltd | 水系樹脂組成物、これを含む水系塗料、その塗料を用いた塗膜、その塗膜を用いた金属板および缶 |
JP2003213201A (ja) * | 2002-01-24 | 2003-07-30 | Toyobo Co Ltd | 塗料用樹脂組成物、およびこれを塗布した塗装金属板 |
JP2004211000A (ja) * | 2003-01-07 | 2004-07-29 | Arakawa Chem Ind Co Ltd | シラン変性ポリエステル樹脂、その製造方法およびコーティング樹脂組成物 |
JP2004346131A (ja) * | 2003-05-20 | 2004-12-09 | Toyobo Co Ltd | ポリエステル樹脂および組成物 |
JP2005194494A (ja) * | 2003-12-09 | 2005-07-21 | Kansai Paint Co Ltd | 水性ポリエステル樹脂組成物の製造方法、該水性ポリエステル樹脂組成物を用いて得られる熱硬化型水性塗料組成物及び該熱硬化型水性塗料組成物を用いて得られる塗装物品 |
JP2006169535A (ja) | 2004-12-17 | 2006-06-29 | Bayer Materialscience Ag | 食品容器用の水性被覆剤 |
JP2013075966A (ja) * | 2011-09-30 | 2013-04-25 | Unitika Ltd | 水性分散体およびその製造方法 |
WO2016072528A1 (ja) * | 2014-11-07 | 2016-05-12 | リケンテクノス株式会社 | ポリエステル系樹脂積層体、及び加飾フィルム |
WO2019111746A1 (ja) * | 2017-12-08 | 2019-06-13 | 東洋紡株式会社 | ポリエステル樹脂、ポリエステル樹脂水分散体、及びポリエステル樹脂水分散体の製造方法 |
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2022
- 2022-07-26 CN CN202280051823.XA patent/CN117751161A/zh active Pending
- 2022-07-26 KR KR1020247007016A patent/KR20240038090A/ko unknown
- 2022-07-26 EP EP22852897.2A patent/EP4382569A1/en active Pending
- 2022-07-26 WO PCT/JP2022/028758 patent/WO2023013474A1/ja active Application Filing
- 2022-07-26 JP JP2023512731A patent/JPWO2023013474A1/ja active Pending
- 2022-08-02 TW TW111128859A patent/TW202309134A/zh unknown
Patent Citations (10)
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JP2001081160A (ja) | 1999-09-13 | 2001-03-27 | Unitika Ltd | 金属缶内面用の被膜形成用共重合ポリエステル樹脂、並びにこれを含有する塗料 |
JP2003089746A (ja) * | 2001-07-06 | 2003-03-28 | Toyobo Co Ltd | 水系樹脂組成物、これを含む水系塗料、その塗料を用いた塗膜、その塗膜を用いた金属板および缶 |
JP2003213201A (ja) * | 2002-01-24 | 2003-07-30 | Toyobo Co Ltd | 塗料用樹脂組成物、およびこれを塗布した塗装金属板 |
JP2004211000A (ja) * | 2003-01-07 | 2004-07-29 | Arakawa Chem Ind Co Ltd | シラン変性ポリエステル樹脂、その製造方法およびコーティング樹脂組成物 |
JP2004346131A (ja) * | 2003-05-20 | 2004-12-09 | Toyobo Co Ltd | ポリエステル樹脂および組成物 |
JP2005194494A (ja) * | 2003-12-09 | 2005-07-21 | Kansai Paint Co Ltd | 水性ポリエステル樹脂組成物の製造方法、該水性ポリエステル樹脂組成物を用いて得られる熱硬化型水性塗料組成物及び該熱硬化型水性塗料組成物を用いて得られる塗装物品 |
JP2006169535A (ja) | 2004-12-17 | 2006-06-29 | Bayer Materialscience Ag | 食品容器用の水性被覆剤 |
JP2013075966A (ja) * | 2011-09-30 | 2013-04-25 | Unitika Ltd | 水性分散体およびその製造方法 |
WO2016072528A1 (ja) * | 2014-11-07 | 2016-05-12 | リケンテクノス株式会社 | ポリエステル系樹脂積層体、及び加飾フィルム |
WO2019111746A1 (ja) * | 2017-12-08 | 2019-06-13 | 東洋紡株式会社 | ポリエステル樹脂、ポリエステル樹脂水分散体、及びポリエステル樹脂水分散体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN117751161A (zh) | 2024-03-22 |
JPWO2023013474A1 (ja) | 2023-02-09 |
TW202309134A (zh) | 2023-03-01 |
EP4382569A1 (en) | 2024-06-12 |
KR20240038090A (ko) | 2024-03-22 |
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