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WO2025164268A1 - Résine polyester, composition de résine polyester, composition de matériau de revêtement, film de revêtement, et boîte métallique - Google Patents

Résine polyester, composition de résine polyester, composition de matériau de revêtement, film de revêtement, et boîte métallique

Info

Publication number
WO2025164268A1
WO2025164268A1 PCT/JP2025/000730 JP2025000730W WO2025164268A1 WO 2025164268 A1 WO2025164268 A1 WO 2025164268A1 JP 2025000730 W JP2025000730 W JP 2025000730W WO 2025164268 A1 WO2025164268 A1 WO 2025164268A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester resin
acid
structural units
mol
units derived
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/000730
Other languages
English (en)
Japanese (ja)
Inventor
弘幸 三枝
英人 五嶋
良輔 神田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo MC Corp
Original Assignee
Toyobo MC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo MC Corp filed Critical Toyobo MC Corp
Publication of WO2025164268A1 publication Critical patent/WO2025164268A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/14—Linings or internal coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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

Definitions

  • the present invention relates to a polyester resin. Specifically, it relates to a polyester resin suitable for use in can coatings, and even more specifically to a polyester resin suitable for coating cans that contain beverages or food, as well as a polyester resin composition, coating composition, coating film, and metal can containing the same.
  • Metal cans such as beverage cans and food cans are coated with organic resins such as polyester to prevent food from corroding the metal (corrosion resistance) and to preserve the flavor and taste of the contents (flavoring).
  • This coating film undergoes high-stress processes such as necking and threading during the molding process for the mouth of a bottle can. Therefore, the coating film must be able to withstand such post-processing (processability).
  • processability Recently, the diversity of can shape designs and can contents has continued to grow, requiring even greater improvements in corrosion resistance and processability from can paints.
  • Patent Document 1 discloses a paint that uses a hydroxyl group-containing polyester resin to provide excellent sterilization stability and flexibility, particularly in acidic media.
  • the hydroxyl group-containing polyester resin described in Patent Document 1 has a low glass transition temperature of -9°C to 40°C, which poses the problem of insufficient corrosion resistance depending on the contents. Furthermore, the molecular weight of the hydroxyl group-containing polyester resin is low, which poses the problem of insufficient processability depending on the part of the can.
  • the present invention provides a polyester resin that has good reactivity with curing agents and can form coating films with excellent processability and corrosion resistance.
  • the present invention comprises the following features:
  • a polyester resin containing a polycarboxylic acid component and a polyhydric alcohol component as copolymerization components which satisfies the following (1) to (3): (1) A glass transition temperature (Tg) of 60°C or higher; (2) A weight average molecular weight (Mw) of 50,000 or higher; (3) A hydroxyl value of the polyester resin of 182 to 800 eq/ton.
  • Tg glass transition temperature
  • Mw weight average molecular weight
  • the polyester resin according to [1] which contains a structural unit derived from an aromatic dicarboxylic acid as the polycarboxylic acid component.
  • the aromatic dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid,
  • the polyester resin according to any one of [2] to [4], wherein the polyester resin contains structural units derived from terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid in a total amount of 50 mol % or more, when the structural units derived from aromatic dicarboxylic acids that constitute the molecular chain of the polyester resin are taken as 100 mol %.
  • the polyester resin according to any one of [1] to [6] which contains structural units derived from a trifunctional or higher polycarboxylic acid and/or structural units derived from a trifunctional or higher polyhydric alcohol, and contains a total of 1.0 mol% or more of the structural units derived from a trifunctional or higher polycarboxylic acid and the structural units derived from a trifunctional or higher polyhydric alcohol when all structural units constituting the molecular chain of the polyester resin are taken as 100 mol%.
  • a metal can containing the coating film according to [14].
  • the present invention provides a polyester resin capable of forming a coating film with excellent processability and corrosion resistance. Therefore, the polyester resin of the present invention is preferably used in applications such as polyester resin compositions, paint compositions, coating films, and metal cans.
  • Polyester resin containing a polycarboxylic acid component and a polyhydric alcohol component as copolymerization components, which satisfies the following (1) to (3): (1)
  • the glass transition temperature (Tg) is 60°C or higher.
  • the weight average molecular weight (Mw) is 50,000 or higher.
  • the hydroxyl value of the polyester resin is 182 to 800 eq/ton.
  • the polyester resin of the present invention is characterized by a high glass transition temperature (Tg) and a high weight-average molecular weight (Mw) (requirements (1) and (2)).
  • Tg glass transition temperature
  • Mw weight-average molecular weight
  • resins with a high glass transition temperature (Tg) often have limited molecular motion and tend to require higher temperatures to relax molecular motion. This results in high melt viscosity during polymerization, which places a heavy burden on equipment, such as increased torque load during stirring, making it difficult to achieve high molecular weight (particularly high Mw).
  • the inventors' investigations have revealed that highly branched polyester resins and increased hydroxyl values within the polyester resins are effective in providing polyester resins with high glass transition temperatures (Tg) and high weight-average molecular weights (Mw) (requirement (3)).
  • polyester resin of the present invention has a high hydroxyl value, which provides many reaction sites with the curing agent. It also has a high glass transition temperature (Tg), which results in good corrosion resistance of the coating film. Furthermore, because the polyester resin also has a high weight-average molecular weight (Mw), the coating film also has good processability.
  • branched structure refers to a branched structure in a polymer chain, and specifically refers to a structure in which three or more branches (molecular chains) extend from a single structural unit that makes up the molecular chain of a polyester resin.
  • a polyester resin has a branched structure, it means that the polymer molecular chain of the polyester resin has, for example, a triester structure, a tetraester structure, or a pentaester structure.
  • Polyester resin has a chemical structure that can be obtained by polycondensation of a polycarboxylic acid component and a polyhydric alcohol component as copolymerization components.
  • all structural units constituting the molecular chain of the polyester resin and "structural units derived from A constituting the molecular chain of the polyester resin” refer to structural units derived from all copolymerization components constituting the molecular chain of the polyester resin, or structural units derived from A, respectively, and do not include structural units derived from a compound having a polycarboxylic acid anhydride group in the molecule that is introduced to the end of the polyester resin after completion of the polycondensation reaction in order to adjust the acid value of the polyester resin.
  • the proportion of each structural unit constituting the polyester resin is determined, for example, from various analyses such as the amount of copolymerization components charged, 1 H-NMR analysis, 13 C-NMR analysis, etc.
  • examples of polycarboxylic acids include tri- or higher functional polycarboxylic acids and dicarboxylic acids.
  • a tri- or higher functional polycarboxylic acid specifically refers to a polycarboxylic acid having three or more carboxy groups, and the number of functional groups is preferably tri- to penta-functional, and more preferably tri- to tetra-functional.
  • a dicarboxylic acid specifically refers to a polycarboxylic acid having two carboxy groups.
  • tri- or higher functional polycarboxylic acids examples include trimellitic acid, pyromellitic acid, trimesic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate), cyclopentane tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butane tetracarboxylic acid, and other polycarboxylic acids and their anhydrides.
  • trimellitic acid trimellitic acid, pyromellitic acid, trimesic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate), and 1,2,3,4-butane tetracarboxylic acid are preferred, with trimellitic acid being more preferred.
  • trimellitic acid being more preferred.
  • trimellitic acid trifunctional or higher polycarboxylic acids
  • those having an aromatic ring such as a benzene ring or a naphthalene ring within the molecule are preferred.
  • polycarboxylic acids having an aromatic ring allows for the introduction of a rigid skeleton within the molecule, which inhibits hydrolysis and facilitates the formation of a coating film with excellent corrosion resistance.
  • dicarboxylic acid examples include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids.
  • aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-furandicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and anhydrides thereof.
  • Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, and anhydrides thereof.
  • Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid, 1,2-cyclohexenedicarboxylic acid, 2,5-norbornanedicarboxylic acid, and anhydrides thereof.
  • examples of polyhydric alcohols include tri- or higher functional polyhydric alcohols and dihydric alcohols.
  • Tri- or higher functional polyhydric alcohols specifically refer to polyhydric alcohols having three or more hydroxy groups, and the number of functional groups is preferably 3 to 5, and more preferably 3 to 4.
  • Dihydric alcohols specifically refer to polyhydric alcohols having two hydroxy groups.
  • trifunctional or higher polyhydric alcohols examples include glycerin, trimethylolethane, trimethylolpropane, mannitol, sorbitol, and pentaerythritol.
  • glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol are preferred, with trimethylolethane being more preferred.
  • dihydric alcohol examples include (a) a dihydric alcohol having one primary hydroxyl group and one secondary hydroxyl group; and (b) a dihydric alcohol other than (a).
  • dihydric alcohol (a) examples include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, etc.
  • 1,2-propanediol and 1,2-butanediol are preferred, and 1,2-propanediol is more preferred.
  • dihydric alcohol (b) examples include aliphatic glycols such as 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-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4-methyl-1,7-heptanediol, 4-methyl-1,8-octanediol, 1,9-nonanediol, and dimer diol; polyether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and polytety
  • the polycarboxylic acid components and polyhydric alcohol components that make up the molecular chains of polyester resins can be derived from biomass resources.
  • Biomass resources include stored materials such as starch and cellulose, which are formed by converting solar energy into plants through photosynthesis, animals that grow by eating plants, and products made by processing plants or animals.
  • plant resources are more preferred, including wood, rice straw, rice husks, rice bran, used rice, corn, sugarcane, cassava, sago palm, soybean pulp, corn cob, tapioca dregs, bagasse, vegetable oil cakes, potatoes, buckwheat, soybeans, oils and fats, waste paper, papermaking residues, seafood residues, livestock excrement, sewage sludge, and food waste.
  • Corn, sugarcane, cassava, and sago palm are even more preferred.
  • polycarboxylic acid raw materials derived from biomass resources include adipic acid, sebacic acid, fumaric acid, itaconic acid, terephthalic acid, and 2,5-furandicarboxylic acid.
  • polyhydric alcohol raw materials derived from biomass resources include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.
  • the polyester resin preferably contains structural units derived from a trifunctional or higher polycarboxylic acid and/or structural units derived from a trifunctional or higher polyhydric alcohol.
  • the structural units derived from a trifunctional or higher polycarboxylic acid and the structural units derived from a trifunctional or higher polyhydric alcohol may be present in a total amount of, for example, 1.0 mol% or more, preferably 1.0 to 6.0 mol%, preferably 1.2 to 6.0 mol%, more preferably 1.5 to 5.0 mol%, and even more preferably 2.0 to 4.0 mol%.
  • the trifunctional or higher polycarboxylic acid and the trifunctional or higher polyhydric alcohol function as branching components in the polyester resin, facilitating the formation of a branched structure.
  • the trifunctional or higher polycarboxylic acid and the trifunctional or higher polyhydric alcohol function as branching components in the polyester resin, facilitating the formation of a branched structure.
  • both trifunctional or higher functional polycarboxylic acids and trifunctional or higher functional polyhydric alcohols can be used as branching components, but it is preferable that the branching components are primarily derived from trifunctional or higher functional polycarboxylic acids.
  • the structural units derived from trifunctional or higher functional polycarboxylic acids and the structural units derived from trifunctional or higher functional polyhydric alcohols are taken as 100 mol%, the structural units derived from trifunctional or higher functional polycarboxylic acids should preferably account for 60 to 100 mol%, more preferably 75 to 99 mol%, and even more preferably 95 to 98 mol%.
  • the polyester resin preferably contains structural units derived from aromatic dicarboxylic acids.
  • the inclusion of structural units derived from aromatic dicarboxylic acids increases the glass transition temperature and improves the corrosion resistance of the coating film.
  • the structural units derived from aromatic dicarboxylic acids are preferably contained in an amount of 60 to 100 mol%, more preferably 65 to 99 mol%, and even more preferably 70 to 98 mol%, based on 100 mol% of the structural units derived from polycarboxylic acids constituting the molecular chain of the polyester resin.
  • the upper limit is not particularly limited, but is preferably 100 mol% or less, more preferably 99 mol% or less, and even more preferably 98 mol% or less. From an industrial perspective, a content below 100 mol% is acceptable.
  • the polyester resin contains, as an aromatic dicarboxylic acid, at least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
  • the structural units derived from aromatic dicarboxylic acids that make up the molecular chain of the polyester resin are taken as 100 mol %
  • the structural units derived from terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid preferably account for a total of 50 to 100 mol %, more preferably 60 to 95 mol %, and even more preferably 70 to 90 mol %.
  • the polyester resin contains, as an aromatic dicarboxylic acid, at least one selected from the group consisting of isophthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, with isophthalic acid and/or orthophthalic acid being more preferable, and orthophthalic acid being even more preferable.
  • isophthalic acid and/or orthophthalic acid being more preferable, and orthophthalic acid being even more preferable.
  • the structural units derived from aromatic dicarboxylic acids that make up the molecular chain of the polyester resin are taken as 100 mol %
  • the structural units derived from at least one component selected from the group consisting of isophthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid preferably account for a total of 1 to 50 mol %, more preferably 5 to 40 mol %, and even more preferably 10 to 30 mol %. By keeping the amount within this range, gelation during polymerization can be effectively suppressed.
  • the polyester resin may contain structural units derived from aliphatic dicarboxylic acids and/or alicyclic dicarboxylic acids.
  • the structural units derived from polycarboxylic acids that make up the molecular chain of the polyester resin are taken as 100 mol %
  • the structural units derived from aliphatic dicarboxylic acids and/or alicyclic dicarboxylic acids preferably account for a total of 20 mol % or less, more preferably 19 mol % or less, even more preferably 18 mol % or less, even more preferably 15 mol % or less, and particularly preferably 10 mol % or less.
  • the polyester resin preferably contains a structural unit derived from a dihydric alcohol (a) having one primary hydroxyl group and one secondary hydroxyl group.
  • the structural unit derived from the polyhydric alcohol constituting the molecular chain of the polyester resin is taken as 100 mol%
  • the structural unit derived from the dihydric alcohol (a) may be, for example, 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
  • the upper limit is not particularly limited, but is preferably 100 mol% or less, and may be, for example, 98 mol% or less, 95 mol% or less, 90 mol% or less, or 80 mol% or less. That is, when the polyhydric alcohol-derived structural units constituting the molecular chain of the polyester resin are taken as 100 mol%, the dihydric alcohol (a)-derived structural units preferably comprise 50 to 100 mol%, 50 to 98 mol%, 50 to 95 mol%, 50 to 90 mol%, 50 to 80 mol%, 60 to 100 mol%, 70 to 100 mol%, 80 to 100 mol%, or 90 to 100 mol%.
  • the polyester resin can also contain, as an optional component, structural units derived from a dihydric alcohol (b) other than the dihydric alcohol (a).
  • structural units derived from polyhydric alcohols that make up the molecular chain of the polyester resin are taken as 100 mol %, the structural units derived from the dihydric alcohol (b) should preferably be 50 mol % or less, more preferably 40 mol % or less, and even more preferably 30 mol % or less, or even 0 mol %.
  • the reaction rate during polymerization of the polyester resin decreases, making it easier to control the reaction and suppressing gelation.
  • the polyester resin can also contain structural units derived from components other than those described above.
  • the polyester resin can also contain structural units derived from components having phenolic hydroxyl groups, such as diphenolic acid, p-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenethyl alcohol, and 5-hydroxyisophthalic acid.
  • phenolic hydroxyl groups do not contribute to the esterification reaction, using such components would likely result in the terminal capping of the polyester resin, making it difficult to adjust the weight-average molecular weight (Mw).
  • the structural units derived from components having phenolic hydroxyl groups are preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 1 mol% or less, and most preferably 0 mol%.
  • the weight-average molecular weight (Mw) can be kept within a preferred range, improving the processability of the coating film.
  • the polyester resin may also contain, for example, structural units derived from components with a molecular weight of 500 or greater.
  • components with a molecular weight of 500 or greater include dimer acid, dimer diol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene, and hydroxyl-terminated polyolefin.
  • a lower copolymerization amount is preferable, and when all structural units constituting the molecular chain of the polyester resin are taken as 100 mol%, the structural units derived from components with a molecular weight of 500 or greater are preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 1 mol% or less, and most preferably 0 mol%.
  • the amount below the upper limit the branched structures (reaction points) in the polymer molecular chain of the polyester resin are closer to each other, resulting in a resin with a higher crosslink density.
  • the weight-average molecular weight (Mw) of the polyester resin is 50,000 or more, desirably 50,000 to 400,000, preferably 51,000 to 400,000, more preferably 55,000 to 350,000, even more preferably 60,000 to 300,000, and still more preferably 70,000 to 280,000, as determined by gel permeation chromatography (GPC) analysis using a polystyrene standard sample.
  • GPC gel permeation chromatography
  • the number average molecular weight (Mn) of the polyester resin is preferably 8,000 to 25,000, more preferably 9,000 to 20,000, and even more preferably 10,000 to 18,000. By keeping it within this range, reactivity with the curing agent is improved, and a coating film with excellent corrosion resistance and processability can be obtained.
  • the molecular weight distribution (Mw/Mn) of the polyester resin is preferably 5.0 to 30.0, more preferably 5.5 to 25.0, and even more preferably 6.5 to 20.0. By keeping it within this range, reactivity with the curing agent is improved, resulting in a coating film with excellent corrosion resistance and processability. Furthermore, because the polyester resin of the present invention has a particularly high weight-average molecular weight (Mw), the molecular weight distribution (Mw/Mn) tends to be large.
  • the hydroxyl value of the polyester resin is 182 to 800 eq/ton, more preferably 190 to 600 eq/ton, and even more preferably 200 to 400 eq/ton. By keeping it within this range, reactivity with the curing agent is improved, and a coating film with excellent corrosion resistance and processability can be obtained.
  • the present invention by increasing the branched structure in the molecular chain of the polyester resin and making the polyester resin highly branched, entanglement of molecular chains is reduced and melt viscosity is lowered.
  • a highly branched polyester resin relatively increases the number of polymer molecular chain ends in the polyester resin, which also increases the hydroxyl value and is preferable from the standpoint of corrosion resistance. Making the polyester resin highly branched also contributes to an improvement in the weight average molecular weight (Mw).
  • the acid value of the polyester resin is, for example, 3 eq/ton or more, desirably 3 to 600 eq/ton, preferably 70 to 600 eq/ton, more preferably 80 to 500 eq/ton, even more preferably 90 to 400 eq/ton, and even more preferably 100 to 350 eq/ton.
  • the acid value of the polyester resin is, for example, 3 eq/ton or more, desirably 3 to 600 eq/ton, preferably 70 to 600 eq/ton, more preferably 80 to 500 eq/ton, even more preferably 90 to 400 eq/ton, and even more preferably 100 to 350 eq/ton.
  • more reaction points with the curing agent can be introduced, increasing the crosslink density.
  • it becomes easier to control the polymerization reaction and a polyester with a higher molecular weight can be obtained.
  • carboxylic acid monoanhydrides include phthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, itaconic anhydride, and citraconic anhydride.
  • trimellitic anhydride is preferred from the viewpoints of versatility and economy.
  • carboxylic acid polyanhydrides include pyromellitic anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, ethylene glycol bistrimellitate dianhydride, and 2,2',3,3'-biphenyltetracarboxylic acid dianhydride. Of these, ethylene glycol bistrimellitate dianhydride is preferred from the standpoint of versatility and economy.
  • the carboxylic acid monoanhydrides and carboxylic acid polyanhydrides may each be used alone or in combination of two or more.
  • the glass transition temperature (Tg) of the polyester resin is 60°C or higher, desirably 60 to 100°C, preferably 62 to 100°C, more preferably 65 to 95°C, and even more preferably 70 to 90°C.
  • Tg glass transition temperature
  • the polyester resin may be either a crystalline resin or an amorphous resin, but is preferably an amorphous resin.
  • the reduced viscosity of the polyester resin is preferably 0.30 to 0.70 dl/g, more preferably 0.35 to 0.65 dl/g, and even more preferably 0.4 to 0.60 dl/g.
  • the manufacturing method of the polyester resin will be described.
  • the esterification/exchange reaction temperature is preferably 180 to 250°C, more preferably 200 to 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 when the desired reaction temperature is reached until the subsequent polycondensation reaction begins.
  • the polyhydric alcohol component is distilled off from the esterified product obtained in the esterification reaction under reduced pressure at a temperature of 220 to 280°C, and the polycondensation reaction is continued until the desired molecular weight is reached.
  • organic titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and titanium oxyacetylcetonate
  • germanium compounds such as germanium dioxide and tetra-n-butoxygermanium
  • antimony compounds such as antimony oxide and tributoxyantimony
  • organic tin compounds such as tin octoate
  • metal acetates such as magnesium, iron, zinc, manganese, cobalt, and aluminum.
  • Organic titanate compounds are preferred in terms of reactivity, while germanium dioxide is preferred in terms of resin coloration.
  • the polyester resin composition of the present invention contains at least the polyester resin and a curing agent. By blending the curing agent, the polyester resin composition can be used as an adhesive, paint, coating agent, etc., and a cured coating film excellent in processability and corrosion resistance can be obtained.
  • curing agent refers to a known curing agent that reacts with polyester resin to form a crosslinked structure.
  • the crosslinked structure include reactions in which unsaturated double bonds in the polyester resin react through radical addition reactions, cationic addition reactions, or anionic addition reactions to form intermolecular carbon-carbon bonds, or intermolecular bonds formed through condensation reactions, polyaddition reactions, or transesterification reactions with polycarboxylic acid groups or polyhydric alcohol groups in the polyester resin.
  • curing agents include polyols such as phenolic resins, amino resins, epoxy compounds, isocyanate compounds, and ⁇ -hydroxylamide compounds, polycarboxylic acids, and unsaturated bond-containing resins. Of these, phenolic resins, amino resins, epoxy compounds, and isocyanate compounds are preferred because they are soluble in both aqueous and organic solvent systems and easily produce cured coatings with high crosslink density.
  • Phenol resins include those synthesized from trifunctional phenolic compounds such as carbolic acid, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol, or bifunctional phenolic compounds such as p-cresol, o-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol, and m-methoxyphenol, and formaldehyde in the presence of an alkaline catalyst, or those in which some or all of the methylol groups have been etherified with a lower alcohol.
  • trifunctional phenolic compounds such as carbolic acid, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol
  • bifunctional phenolic compounds such as p-cresol, o-cresol, p-tert-butylphenol, p-eth
  • Amino resins include formalin adducts of urea, melamine, and benzoguanamine, as well as those etherified by reacting these with lower alcohols.
  • the epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule.
  • Specific examples include glycidyl ether of bisphenol-A and its oligomers, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ester, propylene glycol diglycidyl ester, and 1,4-butanediol diglycidyl ester.
  • Suitable curing catalysts include 1,6-hexanediol diglycidyl ester, polyalkylene glycol diglycidyl esters, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ethers of glycerol alkylene oxide adducts.
  • adducts of glycidyl groups to sorbitol, glycerin, and pentaerythritol are preferred because they are soluble in both aqueous and organic solvent systems and easily produce cured coatings with high crosslink density.
  • Various amine-based catalysts are effective as curing catalysts.
  • isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4 diisocyanate, naphthylene-1,5
  • blocking agents include phenolic compounds such as phenol, cresol, ethylphenol, and butylphenol; alcoholic compounds such as 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, and 2-ethylhexanol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylaceton; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; and acetanilide.
  • phenolic compounds such as phenol, cresol, ethylphenol, and butylphenol
  • alcoholic compounds such as 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-but
  • Suitable amine compounds include acid amide compounds such as amide and acetic acid amide, lactam compounds such as ⁇ -caprolactam, ⁇ -valerolactam, and ⁇ -butyrolactam, imidazole compounds such as imidazole and 2-methylimidazole, urea compounds such as urea, thiourea, and ethyleneurea, oxime compounds such as formamide oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime, and amine compounds such as diphenylaniline, aniline, carbazole, ethyleneimine, and polyethyleneimine. These can be used alone or in combination of two or more types.
  • the reaction between such a blocking agent and an isocyanate curing agent component can be carried out, for example, at 20 to 200°C, using a known inert solvent or catalyst as needed. It is preferable to use 0.7 to 1.5 times the molar amount of the blocking agent relative to the terminal isocyanate groups.
  • the amount of curing agent in the polyester resin composition is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 8 to 30 parts by mass, per 100 parts by mass of polyester resin. By keeping the amount within this range, a coating film with excellent corrosion resistance and processability can be obtained.
  • the reactivity of the polyester resin with the curing agent can also be evaluated by the gel (solvent-insoluble component) fraction.
  • the gel fraction measured by the method described in the examples is preferably 50-100%, more preferably 60-100%, even more preferably 70-98%, and even more preferably 80-98%, with the upper limit being 100%, although it can also be 98% or less. By keeping it within this range, the reactivity with the curing agent is improved, and a coating film with excellent corrosion resistance and processability can be obtained.
  • the coating composition contains at least the polyester resin of the present invention and may further contain an organic solvent.
  • the polyester resin is contained as a main component.
  • the component with the highest content (mass ratio) among the solid components (non-volatile components excluding volatile substances such as water and organic solvents) that form the coating film in the coating composition is defined as the main component.
  • organic solvents examples 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, and Solvesso. Taking into consideration solubility, evaporation rate, etc., these can be used alone or in combination of two or more.
  • the coating composition can contain known additives such as known inorganic pigments such as titanium oxide and silica, phosphoric acid and its esters, surface smoothing agents, antifoaming agents, dispersants, lubricants, crystal nucleating agents, and plasticizers, depending on the required properties.
  • Lubricants are particularly important for imparting the lubricity of the coating film required when molding DI cans, DR (or DRD) cans, etc.
  • Suitable examples of lubricants include fatty acid ester wax, which is an ester of a polyol compound and a fatty acid, silicone wax, fluorine-based wax, polyolefin wax such as polyethylene, lanolin wax, montan wax, and microcrystalline wax. Lubricants can be used alone or in combination of two or more types.
  • resins can be blended into the coating composition to improve the coating film's flexibility, adhesion, etc.
  • examples of other resins include amorphous polyester, crystalline polyester, ethylene-polymerizable unsaturated carboxylic acid copolymer, and ethylene-polymerizable carboxylic acid copolymer ionomer. Blending at least one resin selected from these may impart flexibility and/or adhesion to the coating film.
  • the coating composition can be applied to a metal plate using known coating methods such as roll coating or spray coating. There are no particular restrictions on the coating thickness, but a dry thickness of 3 to 18 ⁇ m, and preferably 5 to 15 ⁇ m, is preferred.
  • the coating is typically baked at temperatures ranging from approximately 120 to 260°C for approximately 5 seconds to 30 minutes, preferably from approximately 140 to 240°C for approximately 10 seconds to 20 minutes.
  • the coating film of the present invention contains at least the coating composition.
  • the coating film refers to a polyester resin layer formed by coating a substrate with the coating composition of the present invention.
  • the coating film may have a configuration in which a coating layer made of a resin other than the polyester resin of the present invention is superimposed on either the top or bottom of the polyester resin layer. That is, the present invention encompasses laminate structures such as substrate/polyester resin layer, substrate/coating layer/polyester resin layer, substrate/polyester resin layer/coating layer, and substrate/coating layer/polyester resin layer/coating layer.
  • the metal can of the present invention contains at least the coating film.
  • Metal cans can be obtained by forming a coating film on one or both sides, and if necessary, on the end faces, of a metal plate made of a metal material that can be used for, for example, beverage cans, canned food cans, their lids, caps, etc. Examples of such metal materials include tinplate, tin-free steel, and aluminum. Metal plates made of these metal materials may be previously subjected to a phosphate treatment, a chromate chromate treatment, a chromate phosphate treatment, or other corrosion prevention treatment using a rust prevention agent, or a surface treatment for improving the adhesion of the coating film.
  • the polyester resin of the present invention can be made into a powder coating by a known pulverization method.
  • known pulverization methods include pulverization.
  • a mixture of the polyester resin composition of the present invention, optionally including an anti-rust pigment and additives is dry-mixed in a mixer such as a tumbler mixer or Henschel mixer, and then melt-kneaded in a kneader.
  • kneaders that can be used include common kneaders such as a single- or twin-screw extruder, a three-roll mill, or a lab blast mill.
  • the kneaded mixture is cooled and solidified, and the solidified product is coarsely and finely pulverized to obtain a pulverized product.
  • pulverizers include jet pulverizers that pulverize using a supersonic jet stream, and impact pulverizers that introduce and pulverize the solidified product into the space formed between a rotor and liner rotating at high speed. If necessary, additives may be added to the pulverized product.
  • the pulverized product is classified to adjust the powder to the desired particle size and particle size distribution, thereby obtaining a powder coating composition.
  • a known classifier that can remove over-pulverized toner base particles by classification using centrifugal force and wind force can be used, such as a rotary wind classifier.
  • Tg Glass Transition Temperature
  • (judgement) ⁇ : (X) - (Y) is 0.1 or more (reduced viscosity is decreased) ⁇ : (X) - (Y) is 0.05 or more and less than 0.1 (reduced viscosity is slightly decreased) ⁇ : (X) - (Y) is 0 or more and less than 0.05 (reduced viscosity remains almost unchanged) ⁇ : (X) - (Y) is less than 0 (reduced viscosity increases over time and gelation is likely to occur during polymerization).
  • the gel fraction was used as an evaluation index of curability.
  • the coating composition was applied to a copper foil so that the thickness after drying was 10 ⁇ m, and heated at 200° C. for 10 minutes to obtain a sample measuring 10 cm in length and 2.5 cm in width.
  • the mass of the sample before immersion in tetrahydrofuran (THF) was (X), and the mass of the sample after immersion in THF (Y) was determined by the following formula.
  • Gel fraction (mass%) [ ⁇ (Y) - mass of copper foil ⁇ / ⁇ (X) - mass of copper foil ⁇ ] x 100
  • test piece was placed upright in a stainless steel cup, and an aqueous solution containing 1 wt % salt and 5 wt % acetic acid was poured into it to reach half the height of the test piece, which was then placed in the pressure cooker of a retort tester (ES-315, manufactured by Tomy Kogyo Co., Ltd.) and subjected to retort treatment at 125°C for 90 minutes.
  • a retort tester ES-315, manufactured by Tomy Kogyo Co., Ltd.
  • Synthesis examples (b) to (r) In Synthesis Examples (b) to (e), (g) to (i), (k) to (m), and (q), polyester resins having the resin compositions shown in the table were produced by transesterification and esterification in the same manner as Synthesis Example (a), except that the charged compositions were changed.
  • Synthesis Example (f) a polyester resin was produced by carrying out the transesterification reaction and esterification reaction in the same manner as in Synthesis Example (a), except that the post-polymerization time was set to 50 minutes.
  • Synthesis Examples (n) to (o) were polymerized in the same manner as Synthesis Example (a), and after the polycondensation reaction was completed, the mixture was cooled to 220°C under a nitrogen atmosphere, and then a predetermined amount of trimellitic anhydride was added and stirred for 30 minutes at 220°C under a nitrogen atmosphere. After the reaction was completed, the mixture was taken out to obtain a polyester resin.
  • Synthesis Example (j) a polyester resin having the resin composition shown in the table was produced by a direct polymerization method (omitting the transesterification reaction step in Synthesis Example (a)).
  • Synthesis Example (p) only the transesterification reaction was carried out, but since gelation occurred when the final polymerization time was 90 minutes, the final polymerization time was set to 50 minutes to produce a polyester resin.
  • Synthesis Example (r) a polyester resin was produced by carrying out the transesterification reaction and esterification reaction in the same manner as in Synthesis Example (a), except that the post-polymerization time was set to 50 minutes.
  • ⁇ Preparation of coating composition 100 parts (solids) of the resulting polyester resin was dissolved in cyclohexanone to obtain a polyester resin solution (solids content approximately 40%). Next, 212.5 parts of the polyester resin solution were blended with 25 parts of an IPDI-based blocked isocyanate (Covestro, DESMODUR VP LS 2078/2, solids content 60 wt%) as a curing agent and 0.1 parts of DBTL (dibutyltin dilaurate) as a catalyst, and then diluted with cyclohexanone to a viscosity suitable for coating to obtain a coating composition. The resulting coating composition was used to evaluate gel fraction, processability, and corrosion resistance.
  • IPDI-based blocked isocyanate Covestro, DESMODUR VP LS 2078/2, solids content 60 wt%
  • DBTL dibutyltin dilaurate
  • ⁇ Preparation of test piece (coating film)> The obtained coating composition was applied to one side of a tinplate (JIS G 3303 (2008) SPTE, 70 mm ⁇ 150 mm ⁇ 0.3 mm) using a bar coater so that the film thickness after drying would be 10 ⁇ 2 ⁇ m, and the coating was baked under baking conditions of 200°C ⁇ 10 minutes to prepare a test piece (coating film).
  • a tinplate JIS G 3303 (2008) SPTE, 70 mm ⁇ 150 mm ⁇ 0.3 mm
  • Comparative Example 1 Although the glass transition temperature (Tg) was high, the hydroxyl value was low and the polyester resin did not have a sufficient branched structure, making it difficult to increase the weight average molecular weight (Mw).
  • the weight average molecular weight (Mw) of the polyester resin was low, resulting in poor processability of the coating film. Furthermore, because the hydroxyl value was low, there were insufficient reaction sites with the curing agent, and the resulting polyester resin had poor reactivity with the curing agent, resulting in poor corrosion resistance of the coating film.
  • Comparative Example 2 the weight average molecular weight (Mw) of the polyester resin was low, and as a result, the coating film had poor processability.
  • the present invention relates to a polyester resin that has good reactivity with a curing agent and can form a coating film that is excellent in processability and corrosion resistance, and a polyester resin composition containing the polyester resin of the present invention is applicable to various uses.
  • the polyester resin of the present invention can be effectively used in the form of a paint composition, an adhesive composition, a coating composition, etc., and is preferably used as a base agent for a paint for coating metal cans that contain beverages or foods.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention fournit une résine polyester qui présente une réactivité satisfaisante vis-à-vis d'un agent de durcissement, et qui permet de former un film de revêtement excellent en termes d'usinabilité et de résistance à la corrosion.　Plus précisément, l'invention concerne une résine polyester dans laquelle un composant acide carboxylique polyvalent et un composant alcool polyvalent servent de composants copolymère, et qui satisfait les points (1) à (3) suivants. (1) La température de transition vitreuse (Tg) est supérieure ou égale à 60°C. (2) La masse moléculaire moyenne en poids (Mw) est supérieure ou égale à ５００００. (3) L'indice d'hydroxyle de la résine polyester est compris entre 182 et ８００éｑ／tonne.
PCT/JP2025/000730 2024-01-31 2025-01-10 Résine polyester, composition de résine polyester, composition de matériau de revêtement, film de revêtement, et boîte métallique Pending WO2025164268A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11236529A (ja) * 1998-02-20 1999-08-31 Unitika Ltd 水系塗料組成物、その製造方法及びそれから得られる塗膜
US20080124644A1 (en) * 2006-11-13 2008-05-29 Yongning Liu Polyester Toner Resin Compositions
JP2010059266A (ja) * 2008-09-02 2010-03-18 Unitika Ltd ポリエステル樹脂水性分散体の製造方法
JP2011524451A (ja) * 2008-06-16 2011-09-01 ビーエーエスエフ ソシエタス・ヨーロピア ポリマー製造のための、ｃ１１ジオール、又はｃ１１ジオール混合物の使用
WO2011132318A1 (fr) * 2010-04-23 2011-10-27 日華化学株式会社 Résine de polyester amorphe, résine liante pour toner pour le développement d'image électrostatique et procédé de production de résine de polyester amorphe
JP2012001636A (ja) * 2010-06-17 2012-01-05 Unitika Ltd コーティング剤およびそれを用いた積層フィルム
US20170022387A1 (en) * 2013-11-29 2017-01-26 Ppg Industries Ohio, Inc. Coating Composition
JP2018141967A (ja) * 2017-02-28 2018-09-13 三洋化成工業株式会社 トナーバインダー及びトナー
JP2021050321A (ja) * 2019-09-17 2021-04-01 三洋化成工業株式会社 トナー用ポリエステル樹脂及びトナーの製造方法
JP2023058877A (ja) * 2021-10-14 2023-04-26 Dic株式会社 接着剤、電池用包装材用接着剤、積層体、電池用包装材、電池用容器及び電池

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11236529A (ja) * 1998-02-20 1999-08-31 Unitika Ltd 水系塗料組成物、その製造方法及びそれから得られる塗膜
US20080124644A1 (en) * 2006-11-13 2008-05-29 Yongning Liu Polyester Toner Resin Compositions
JP2011524451A (ja) * 2008-06-16 2011-09-01 ビーエーエスエフ ソシエタス・ヨーロピア ポリマー製造のための、ｃ１１ジオール、又はｃ１１ジオール混合物の使用
JP2010059266A (ja) * 2008-09-02 2010-03-18 Unitika Ltd ポリエステル樹脂水性分散体の製造方法
WO2011132318A1 (fr) * 2010-04-23 2011-10-27 日華化学株式会社 Résine de polyester amorphe, résine liante pour toner pour le développement d'image électrostatique et procédé de production de résine de polyester amorphe
JP2012001636A (ja) * 2010-06-17 2012-01-05 Unitika Ltd コーティング剤およびそれを用いた積層フィルム
US20170022387A1 (en) * 2013-11-29 2017-01-26 Ppg Industries Ohio, Inc. Coating Composition
JP2018141967A (ja) * 2017-02-28 2018-09-13 三洋化成工業株式会社 トナーバインダー及びトナー
JP2021050321A (ja) * 2019-09-17 2021-04-01 三洋化成工業株式会社 トナー用ポリエステル樹脂及びトナーの製造方法
JP2023058877A (ja) * 2021-10-14 2023-04-26 Dic株式会社 接着剤、電池用包装材用接着剤、積層体、電池用包装材、電池用容器及び電池

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