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WO2015045633A1 - Copolyester cristallin, dispersion aqueuse de résine de polyester, et agent de thermoscellage utilisant celle-ci - Google Patents

Copolyester cristallin, dispersion aqueuse de résine de polyester, et agent de thermoscellage utilisant celle-ci Download PDF

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Publication number
WO2015045633A1
WO2015045633A1 PCT/JP2014/070697 JP2014070697W WO2015045633A1 WO 2015045633 A1 WO2015045633 A1 WO 2015045633A1 JP 2014070697 W JP2014070697 W JP 2014070697W WO 2015045633 A1 WO2015045633 A1 WO 2015045633A1
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Prior art keywords
polyester resin
parts
mol
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component
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English (en)
Japanese (ja)
Inventor
貴洋 服部
泰伸 須堯
雅人 谷川
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2015539004A priority Critical patent/JP6439984B2/ja
Publication of WO2015045633A1 publication Critical patent/WO2015045633A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a crystalline copolyester resin and an aqueous polyester resin dispersion. More specifically, the present invention relates to a heat sealing agent having a polyester resin aqueous dispersion as a main component and particularly excellent in water resistance and boiling water resistance.
  • Copolyester resin is widely used as a raw material for resin compositions used for paints, coating agents, adhesives and the like.
  • the copolyester resin is generally composed of a polyvalent carboxylic acid and a polyhydric alcohol. Selection and combination of polyvalent carboxylic acid and polyhydric alcohol, the molecular weight can be freely controlled, and the resulting copolyester resin is used in various applications including paint and adhesive applications.
  • copolymer polyester resin In the molecular design of copolymer polyester resin, the selection of copolymer components is important.
  • the polyvalent carboxylic acid component and the polyhydric alcohol component are roughly classified into aromatic, aliphatic and alicyclic groups. By selecting these components, the glass transition temperature showing the flexibility of the copolyester resin can be determined.
  • organic solvent-dissolved products and water-dispersed products are generally used by being applied to a substrate, but in recent years, aqueous dispersions have been required due to environmental problems.
  • Patent Document 1 proposes an aqueous dispersion using a polyester resin having an acid value of 8 KOHmg / g or more.
  • the acid value of the polyester resin is high, the molecular weight is limited, and as a result, there is a problem that the adhesiveness is insufficient.
  • Patent Document 2 proposes an aqueous polyester resin dispersion containing two types of polyester resins having different number average molecular weights and glass transition temperatures.
  • an aqueous polyester resin dispersion when used as a heat sealant, it is often used in food packaging materials, and the process of performing moisture treatment and sterilization treatment on the contents can change the appearance of the packaging material and the contents. From the aspect of influence, excellent water resistance and boiling water resistance are required.
  • this invention is providing the heat-sealing agent which has as a main component the crystalline copolymerization polyester resin shown below, a polyester resin aqueous dispersion, and a polyester resin aqueous dispersion.
  • a polyhydric carboxylic acid component and a polyhydric alcohol component are used as a copolymerization component, an ethylene glycol component is 25 mol% or less as a polyhydric alcohol component, and a linear aliphatic diol component having 4 to 10 carbon atoms is 75 mol%.
  • the crystalline copolyester resin (A) contains, as a polyvalent carboxylic acid component, an aromatic dicarboxylic acid having a sulfonic acid metal salt in a range of 2 mol% to 5 mol%, and an acid value of 4 KOHmg / It is preferable that it is less than g.
  • Polyester resin aqueous dispersion (C) for heat sealant containing 180 to 550 parts by weight of water and 15 to 200 parts by weight of organic solvent with respect to 100 parts by weight of the crystalline copolyester resin (A).
  • an aromatic dicarboxylic acid having a sulfonic acid metal salt is contained in the range of 2 mol% to 8 mol%, and the amorphous copolymer
  • a heat sealant comprising the polyester resin aqueous dispersion (C) or the polyester resin aqueous dispersion (D) as a main component.
  • a heat seal layer produced using the heat sealant is A heat seal layer produced using the heat sealant.
  • a laminate of the heat seal layer and a polyester film, polyolefin film or polyamide film is provided.
  • the heat sealant using the crystalline copolyester resin and the polyester resin aqueous dispersion of the present invention is excellent in water resistance and boiling water resistance, and impairs the function as a packaging material due to the boiling water resistance during sterilization treatment. It is possible to provide a packaging material with excellent durability.
  • the crystalline copolyester resin (A) in the present invention has a chemical structure that can be obtained by a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. It consists of two or more selected components.
  • the polyester resin needs to have heat resistance in order to exhibit excellent boiling water resistance.
  • having a melting point that is, crystallinity is an important factor.
  • crystallinity it is necessary to design the polyester resin using a linear raw material.
  • hydrolysis resistance of the polyester resin itself that is, a linear aliphatic diol having 4 to 10 carbon atoms, which has an ethylene glycol component inferior in hydrolysis resistance as a polyhydric alcohol component, suppressed to a low copolymerization amount of 25 mol% or less and excellent in hydrolysis resistance.
  • aromatic dicarboxylic acid As the polyvalent carboxylic acid constituting the crystalline copolyester resin (A) of the present invention, aromatic dicarboxylic acid, aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid are preferable, and among them, aromatic dicarboxylic acid and / or Aliphatic dicarboxylic acids are more preferred.
  • the copolymerization amount of the aromatic dicarboxylic acid component is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 50 mol% or more, and 55 mol when the total amount of the carboxylic acid components is 100 mol%. % Or more is particularly preferable, and 60 mol% or more is most preferable.
  • the amount is too small, the mechanical strength of the resulting coating film may be lowered. Moreover, 90 mol% or less is preferable, 85 mol% or less is more preferable, and 80 mol% or less is more preferable. If the amount is too large, the polyester resin becomes amorphous, and the heat resistance of the polyester resin may decrease.
  • the copolymerization amount of the aliphatic dicarboxylic acid is preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less, and more preferably 25 mol% when the total amount of carboxylic acid components is 100 mol%.
  • the following are particularly preferred: If the amount is too large, the hydrolysis resistance of the polyester resin deteriorates, and the water resistance and boiling water resistance may decrease. Moreover, 10 mol% or more is preferable, 15 mol% or more is more preferable, and 20 mol% or more is further more preferable. If the amount is too small, the polyester resin becomes amorphous, and the heat resistance of the polyester resin may decrease.
  • the aromatic dicarboxylic acid is not particularly limited.
  • Examples include sodium methoxybenzene sulfonate, lithium 3,5-dicarbomethoxybenzene sulfonate, and potassium 3,5-dicarbomethoxybenzene sulfonate, among which terephthalic acid, isophthalic acid, 3,5-dicarbomethoxybenzene sulfone.
  • Sodium acid is preferred.
  • the alicyclic dicarboxylic acid is not particularly limited.
  • 1,4-cyclohexanedicarboxylic acid 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, tetrahydrophthalic acid Etc.
  • aliphatic dicarboxylic acid examples include, but are not limited to, for example, oxalic acid, malonic acid, succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid, Examples thereof include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid and the like, and among them, adipic acid and sebacic acid are preferable. These can be used alone or in combination of two or more.
  • a sulfonic acid metal salt into the crystalline copolyester resin (A), and it is more preferable to introduce an alkali metal sulfonate.
  • the sulfonic acid metal salt By introducing the sulfonic acid metal salt, the hydrophilicity of the polyester resin is increased, so that an aqueous dispersion can be obtained.
  • the copolymer component having a sulfonic acid metal salt is not particularly limited, but an aromatic dicarboxylic acid having a sulfonic acid metal salt is preferable, and an aromatic dicarboxylic acid having a sulfonic acid alkali metal salt is more preferable.
  • Specific examples include, but are not limited to, monosodium 5-sulfoisophthalate, monopotassium 5-sulfoisophthalate, monosodium 2-sulfoterephthalate, monopotassium 2-sulfoterephthalate, monosodium 4-sulfophthalate, 4 -Monopotassium sulfophthalate, lithium 3,5-dicarbomethoxybenzenesulfonate, sodium 3,5-dicarbomethoxybenzenesulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, etc.
  • monosodium 5-sulfoisophthalate monopotassium 5-sulfoisophthalate
  • monopotassium 5-sulfoisophthalate monosodium 2-sulfoterephthalate
  • monopotassium 2-sulfoterephthalate monosodium 4-sulfophthalate
  • 4 -Monopotassium sulfophthalate lithium 3,5-dicar
  • the aromatic dicarboxylic acid having a sulfonic acid metal salt is preferably 2 mol% or more, more preferably 2.2 mol% or more, and more preferably 2.5 mol% or more when the total amount of carboxylic acid components is 100 mol%. Further preferred. If it is less than 2 mol%, water dispersion and storage stability may be hindered. Moreover, 5 mol% or less is preferable, 4.5 mol% or less is more preferable, and 4 mol% or less is more preferable. If it is higher than 5 mol%, the hydrophilicity of the resin becomes too high, and the water resistance and boiling water resistance may decrease. By making it contain in the said range, the aqueous dispersion of a polyester resin can be obtained efficiently.
  • the polyhydric alcohol component constituting the crystalline copolyester resin (A) of the present invention when the total amount of diol components is 100 mol%, the ethylene glycol component must be 25 mol% or less.
  • the content is preferably 23 mol% or less, more preferably 20 mol% or less, still more preferably 18 mol% or less, particularly preferably 15 mol% or less, and most preferably 10 mol% or less. If the amount is too large, water resistance and boiling water resistance may decrease, and storage stability as an aqueous dispersion may decrease.
  • the linear aliphatic diol component having 4 to 10 carbon atoms needs to be 75 mol% or more, preferably It is 78 mol% or more, more preferably 80 mol% or more, further preferably 78 mol% or more, particularly preferably 75 mol% or more, and most preferably 90 mol% or more.
  • the larger the amount of copolymerization the more preferable crystallization progresses and the heat resistance is improved. If the amount is too small, the water resistance and boiling water resistance are lowered, and the storage stability as an aqueous dispersion may be lowered. .
  • the linear aliphatic diol component having 4 to 10 carbon atoms is not particularly limited, and examples thereof include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptane.
  • Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol and the like can be mentioned, and these can be used alone or in combination of two or more.
  • 1,4-butanediol and 1,6-hexanediol are particularly preferred from the viewpoint of ease of formation of crystallinity and design of a melting point of 90 ° C. or higher and 130 ° C. or lower. These can be used alone or in combination of two or more.
  • Examples of other polyhydric alcohol components constituting the crystalline copolyester resin (A) of the present invention include aliphatic polyhydric alcohols such as propylene glycol and 1,3-propanediol, and 1,4-cyclohexanedimethanol. , Aromatic groups such as alicyclic polyhydric alcohols such as tricyclodecane dimethanol, polyalkylene ether glycols such as diethylene glycol and triethylene glycol, and ethylene oxide adducts of 4,4′-bisphenols such as bisphenol A and bisphenol F Polyhydric alcohols having can be used.
  • the branched aliphatic diol component having 4 to 10 carbon atoms is preferably 20 mol% or less, more preferably 15 mol% or less. More preferably 10 mol% or less, particularly preferably 5 mol% or less, and most preferably 0 mol%. If the branched aliphatic diol component having 4 to 10 carbon atoms is too much, the crystallinity is lowered, and therefore, the boiling water resistance may be lowered.
  • the branched aliphatic diol component having 4 to 10 carbon atoms is not particularly limited, and examples thereof include neopentyl glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, and 1,2-butane.
  • Diol, 3-methyl-1,5-pentanediol, 1-methyl-1,8-octanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propane Diol etc. are mentioned.
  • the crystalline copolymer polyester resin (A) of the present invention may be copolymerized with a trivalent or higher polyvalent carboxylic acid and / or a trivalent or higher polyhydric alcohol component.
  • a trivalent or higher polyvalent carboxylic acid component include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and trimesic acid, and aliphatic dicarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid. An acid etc. are mentioned.
  • the trihydric or higher polyhydric alcohol component is not particularly limited, and examples thereof include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol, and sorbitol. It can be used in combination.
  • the crystallinity referred to in the present invention means that a temperature is raised from ⁇ 50 ° C. to 200 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and shows a clear melting peak in the temperature raising process. Point to.
  • DSC differential scanning calorimeter
  • the melting point of the crystalline copolyester resin (A) of the present invention needs to be 90 ° C. or higher, preferably 92 ° C. or higher, more preferably 94 ° C. or higher, and still more preferably 96 ° C. or higher. Especially preferably, it is 98 degreeC or more, Most preferably, it is 100 degreeC or more.
  • the melting point is less than 90 ° C., the heat resistance is lowered and the boiling water resistance may be inferior. Further, it must be 130 ° C. or lower, preferably 129 ° C. or lower, more preferably 128 ° C. or lower, still more preferably 127 ° C. or lower, particularly preferably 126 ° C. or lower, most preferably 125 ° C.
  • the melting point is higher than 130 ° C.
  • heat sealing needs to be performed at a high temperature, and when a plastic film such as a polyester film is used as a base material to be applied, problems such as deformation of the base material may occur.
  • the heat seal temperature is lowered, the resin does not melt and a sealing failure may occur. From the viewpoint of imparting heat resistance and an appropriate heat seal temperature, the melting point needs to be 90 ° C. or higher and 130 ° C. or lower.
  • the acid value of the crystalline copolyester resin (A) of the present invention is preferably less than 4 KOH mg / g, more preferably less than 3 KOH mg / g, still more preferably less than 2 KOH mg / g, and 1 KOH mg / g. Particularly preferred is less than g, and most preferred is 0 KOH mg / g. If the acid value is too large, the decomposition of the resin is accelerated, and the storage stability of water resistance, boiling water resistance and water dispersion may be lowered.
  • the number average molecular weight of the crystalline copolyester resin (A) of the present invention is not particularly limited, but is preferably 4,000 or more, more preferably 6,000 or more, and 8,000 or more. Is more preferable.
  • the number average molecular weight is less than 4,000, when used in a heat sealant, only low adhesive strength, water resistance, and boiling water resistance may be obtained due to low cohesion.
  • an upper limit is not specifically limited, It is preferable that it is 30,000 or less, and it is more preferable that it is 25,000 or less. If it is too large, an aqueous dispersion may not be prepared.
  • the crystalline copolyester resin (A) of the present invention contains a known additive such as an epoxy compound or a carbodiimide compound within a range not impairing the effects of the present invention. Can do.
  • the crystalline copolyester resin (A) of the present invention can be suitably used as a raw material for adhesives, coating agents and heat sealants, and is particularly suitable for heat sealant applications.
  • the amorphous copolyester resin (B) used in the present invention has a chemical structure that can be obtained by a polycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol. It consists of seeds or two or more selected components.
  • the polyvalent carboxylic acid constituting the amorphous copolyester resin (B) used in the present invention is preferably an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid, and more preferably an aromatic dicarboxylic acid. More preferred.
  • the copolymerization amount of the aromatic dicarboxylic acid component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, and 95 mol when the total amount of carboxylic acid components is 100 mol%. % Or more is particularly preferable, and 100 mol% is most preferable. If the amount is too small, the boiling water resistance may decrease.
  • the aromatic dicarboxylic acid is not particularly limited.
  • examples thereof include sodium methoxybenzenesulfonate, and among them, terephthalic acid, isophthalic acid, and sodium 3,5-dicarbomethoxybenzenesulfonate are preferable. These can be used alone or in combination of two or more.
  • a sulfonic acid metal salt into the amorphous copolymerized polyester resin (B), and it is more preferable to introduce an alkali metal sulfonate.
  • the sulfonic acid metal salt By introducing the sulfonic acid metal salt, the hydrophilicity of the polyester resin is increased, so that an aqueous dispersion can be obtained.
  • the copolymer component having a sulfonic acid metal salt is not particularly limited, but an aromatic dicarboxylic acid having a sulfonic acid metal salt is preferable, and an aromatic dicarboxylic acid having a sulfonic acid alkali metal salt is more preferable.
  • Specific examples include, but are not limited to, monosodium 5-sulfoisophthalate, monopotassium 5-sulfoisophthalate, monosodium 2-sulfoterephthalate, monopotassium 2-sulfoterephthalate, monosodium 4-sulfophthalate, 4 -Monopotassium sulfophthalate, lithium 3,5-dicarbomethoxybenzenesulfonate, sodium 3,5-dicarbomethoxybenzenesulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, etc.
  • monosodium 5-sulfoisophthalate monopotassium 5-sulfoisophthalate
  • monopotassium 5-sulfoisophthalate monosodium 2-sulfoterephthalate
  • monopotassium 2-sulfoterephthalate monosodium 4-sulfophthalate
  • 4 -Monopotassium sulfophthalate lithium 3,5-dicar
  • the aromatic dicarboxylic acid having a sulfonic acid metal salt is preferably 2 mol% or more, more preferably 2.2 mol% or more, and more preferably 2.5 mol% or more when the total amount of carboxylic acid components is 100 mol%. Further preferred. If the amount is too small, it may interfere with water dispersion and storage stability. Moreover, 8 mol% or less is preferable, 7 mol% or less is more preferable, and 6 mol% or less is more preferable. When the amount is too large, decomposition of the resin is accelerated, and the storage stability of water resistance, boiling water resistance and water dispersion may be lowered. By making it contain in the said range, the aqueous dispersion of a polyester resin can be obtained efficiently.
  • amorphous as used in the present invention means that the temperature is raised from ⁇ 50 ° C. to 200 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and no clear melting peak is shown in the temperature raising process. Refers to things.
  • the glass transition temperature of the amorphous copolymerized polyester resin (B) needs to be 40 ° C. or higher, preferably 45 ° C. or higher, and more preferably 50 ° C. or higher.
  • the temperature is lower than 40 ° C., the heat resistance may be lowered, resulting in inferior boiling water resistance or problems such as blocking during winding.
  • it is necessary that it is 80 degrees C or less, it is preferable that it is 75 degrees C or less, and it is more preferable that it is 70 degrees C or less. If it is higher than 80 ° C., the resin does not melt sufficiently during heat sealing, and sealing failure may occur.
  • the acid value of the amorphous copolymerized polyester resin (B) is preferably less than 4 KOH mg / g, more preferably 3 KOH mg / g or less, still more preferably 2 KOH mg / g or less, and 1 KOH mg / g or less. Particularly preferred is 0 KOH mg / g. When it is 4 KOHmg / g or more, the decomposition of the resin is promoted, and the storage stability of water resistance, boiling water resistance and water dispersion may be lowered.
  • conventionally known polymerization catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, titanium Titanium compounds such as oxyacetylcetonate, antimony compounds such as antimony trioxide and tributoxyantimony, germanium compounds such as germanium oxide and tetra-n-butoxygermanium, and others such as magnesium, iron, zinc, manganese, cobalt, and aluminum Acetate can be used.
  • These catalysts can be used alone or in combination of two or more.
  • the method of the polymerization condensation reaction for producing the crystalline copolymer polyester resin (A) and the amorphous copolymer polyester resin (B) of the present invention is not particularly limited.
  • a method of performing depolyhydric alcohol / polycondensation reaction through heating and transesterification In the methods 1) and 2), part or all of the acid component may be substituted with an acid anhydride.
  • the aqueous polyester resin dispersion (C) of the present invention is an aqueous dispersion containing the crystalline copolyester resin (A), water and an organic solvent.
  • the boiling point of the organic solvent used in the aqueous polyester resin dispersion (C) of the present invention is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, further preferably 110 ° C. or higher, and 115 ° C. or higher. It is particularly preferable that the temperature is 120 ° C. or higher. If the boiling point is less than 100 ° C., the crystalline copolyester cannot be melted, so that it may be difficult to disperse in water. Therefore, many polyester resin aggregates generate
  • boiling point is higher than 180 ° C., a large amount of residual solvent remains during drying, which may cause problems such as blocking during winding.
  • the organic solvent used in the aqueous polyester resin dispersion (C) of the present invention is not particularly limited, but alcohols such as isobutyl alcohol and isoamino alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether (hereinafter also referred to as “n-butyl cellosolve” or “n-BuCS”), ethylene glycol mono-tert-butyl ether (hereinafter also referred to as “t-butyl cellosolve” or “t-BuCS”), propylene Examples include glycol monobutyl ether. These organic solvents can be used alone or in combination of two or more. Of these, n-butyl cellosolve and t-butyl cellosolve are particularly preferred.
  • the organic solvent is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 25 parts by mass or more with respect to 100 parts by mass of the crystalline copolyester resin (A).
  • the amount is preferably 30 parts by mass or more. If the amount is too small, the resin particle diameter of the polyester may become coarse, so that the water dispersibility is inferior and a large amount of polyester resin agglomerates may be generated. Further, it is preferably 200 parts by mass or less, more preferably 190 parts by mass or less, further preferably 180 parts by mass or less, and particularly preferably 170 parts by mass or less. If the amount is too large, a large amount of residual solvent remains during drying, which may cause problems such as blocking during winding.
  • Water is preferably 180 parts by mass or more, more preferably 190 parts by mass or more, and further preferably 200 parts by mass or more with respect to 100 parts by mass of the crystalline copolyester resin (A). . If the amount is too small, the polyester resin may not be dispersed in water, and an aqueous polyester resin dispersion may not be obtained. Further, it is preferably 550 parts by mass or less, more preferably 530 parts by mass or less, and further preferably 500 parts by mass or less. If the amount is too large, the production efficiency may be lowered and may not be practical.
  • the particle diameter of the polyester resin phase contained in the aqueous polyester resin dispersion (C) according to the present invention is preferably 30 nm or more, more preferably 40 nm or more, further preferably 50 nm or more, and particularly preferably 60 nm or more. If it is too small, the film-forming property tends to be improved. Therefore, fusion and aggregation between dispersed particles are likely to occur, and as a result, the possibility of causing thickening and poor dispersion is increased, which is not preferable. Moreover, 250 nm or less is preferable, 200 nm or less is more preferable, and 150 nm or less is more preferable.
  • the particle diameter refers to the particle diameter of the crystalline copolyester resin (A), and further contains two or more types of polyester resins, such as containing other polyester resins. Refers to the average particle size of the polyester resin.
  • the aqueous polyester resin dispersion (C) of the present invention can be suitably used as a raw material for adhesives, coating agents and heat sealants, and is particularly suitable for heat sealant applications.
  • the aqueous polyester resin dispersion (D) of the present invention comprises the crystalline copolymer polyester resin (A) and the amorphous copolymer polyester resin (B), water and an organic solvent having a boiling point of 100 ° C. or higher and 180 ° C. or lower.
  • An aqueous dispersion containing. Adhesiveness after heat sealing can be improved by mixing two types of copolyester resins.
  • amorphous copolymer polyester resin (B) with respect to 100 parts by mass of crystalline copolymer polyester resin (A), more preferably 50 parts by mass or more, and 60 parts by mass. More preferably, it is more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more. If the amount is too small, the adhesiveness after heat sealing is lowered, and the bag may be broken in normal handling or the boiling water resistance may be lowered.
  • blend 250 mass parts or less it is preferable to mix
  • the boiling point of the organic solvent used in the aqueous polyester resin dispersion (D) of the present invention must be 100 ° C. or higher, preferably 105 ° C. or higher, more preferably 110 ° C. or higher, and 115 ° C. or higher. More preferably, it is particularly preferably 120 ° C. or higher. If the boiling point is less than 100 ° C., the crystalline copolyester cannot be melted, so that it may be difficult to disperse in water. Therefore, many polyester resin aggregates generate
  • the organic solvent used in the aqueous polyester resin dispersion (D) of the present invention is not particularly limited, and examples thereof include alcohols such as isobutyl alcohol and isoamino alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoisopropyl.
  • n-butyl cellosolve and t-butyl cellosolve are particularly preferred.
  • the organic solvent is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and further preferably 50 parts by mass or more with respect to 100 parts by mass of the crystalline copolyester resin (A). It is preferably 60 parts by mass or more. If the amount is too small, the resin particle diameter of the polyester may become coarse, so that the water dispersibility is inferior and a large amount of polyester resin agglomerates may be generated. Moreover, it is preferably 400 parts by mass or less, more preferably 380 parts by mass or less, further preferably 360 parts by mass or less, and particularly preferably 340 parts by mass or less. If the amount is too large, a large amount of residual solvent remains during drying, which may cause problems such as blocking during winding.
  • Water is preferably 360 parts by mass or more, more preferably 380 parts by mass or more, and further preferably 400 parts by mass or more with respect to 100 parts by mass of the crystalline copolyester resin (A). . If the amount is too small, the polyester resin may not be dispersed in water, and an aqueous polyester resin dispersion may not be obtained. Further, it is preferably 1100 parts by mass or less, more preferably 1050 parts by mass or less, and further preferably 1000 parts by mass or less. If the amount is too large, the production efficiency may be lowered and may not be practical.
  • the aqueous polyester resin dispersion (D) of the present invention can further contain isopropyl alcohol.
  • isopropyl alcohol is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the crystalline copolyester resin (A). Further preferred. Moreover, it is preferable that it is 200 mass parts or less, It is more preferable that it is 150 mass parts or less, It is further more preferable that it is 100 mass parts or less. If the amount is too large, the stability of the aqueous polyester resin dispersion may decrease.
  • the production method of the polyester resin aqueous dispersion (D) is not particularly limited.
  • 1) The crystalline copolymer polyester resin (A) and the amorphous copolymer polyester resin (B) are mixed in advance.
  • a method of aqueous dispersion after preparing a polyester resin composition 2) An aqueous polyester resin dispersion (C) containing a crystalline copolyester resin (A), and an amorphous copolyester resin
  • the method 2) is preferred because of the ease of production.
  • other polyester resins or aqueous dispersions may be mixed within a range not impairing the performance of the present invention.
  • the particle diameter of the polyester resin phase contained in the aqueous polyester resin dispersion (D) according to the present invention is preferably 30 nm or more, more preferably 40 nm or more, further preferably 50 nm or more, and particularly preferably 60 nm or more. If it is too small, the film-forming property tends to be improved. Therefore, fusion and aggregation between dispersed particles are likely to occur, and as a result, the possibility of causing thickening and poor dispersion is increased, which is not preferable. Moreover, 250 nm or less is preferable, 200 nm or less is more preferable, and 150 nm or less is more preferable.
  • the particle diameter refers to the average particle diameter of the crystalline copolyester resin (A) and the amorphous copolyester resin (B), and further contains other polyester resins, such as three or more types of polyester resins. Is contained, the average particle diameter of three or more types of polyester resins is indicated.
  • the aqueous polyester resin dispersion (D) of the present invention can be suitably used as a raw material for adhesives, coating agents and heat sealants, and is particularly suitable for heat sealant applications.
  • the heat sealing agent of the present invention is mainly composed of the polyester resin aqueous dispersion (C) or the polyester resin aqueous dispersion (D).
  • the heat seal layer produced using the heat sealant obtained from the aqueous fraction has water resistance, Excellent boiling water.
  • the amount of the polyester resin aqueous dispersion (C) or the polyester resin aqueous dispersion (D) in the entire heat sealant is preferably 50% by mass or more, and 60% by mass. % Or more, more preferably 70% by mass or more.
  • the heat sealing agent of the present invention may be used by blending various additives in addition to the aqueous polyester resin dispersion (C) or the aqueous polyester resin dispersion (D) within a range not impairing the performance of the present invention. it can. Although it does not specifically limit as an additive, It is preferable to use a flame retardant, a filler, a pigment, an antiblocking agent, etc.
  • fillers and / or pigments that can be added to the heat sealant of the present invention are not particularly limited, but include titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, aluminum oxide, kaolin clay, carbon black.
  • Inorganic fillers such as calcium silicate, water-dispersed silica, fumed silica, phthalocyanine blue, phthalocyanine green, carbazole dioxazine violet, anthrapyrimidine yellow, isoindolinone Yellow, mention may be made of an organic pigment, such as the Indus Ren blue. These fillers and / or pigments can be used alone or in combination of two or more.
  • the heat sealant of the present invention has good water resistance and boiling water resistance, it can be suitably used for packaging bags for foodstuffs such as vegetables and lids for jelly cups.
  • the heat seal layer of the present invention is obtained by applying the heat seal agent on a substrate and then performing a drying treatment.
  • the application amount of the heat sealant is preferably adjusted so that the thickness of the heat seal layer is 1 to 30 ⁇ m.
  • the substrate is not particularly limited, and examples thereof include a polyester film, a polyolefin film, a polyamide film, a poval film, a PET film, a polyvinyl chloride film, and a polyurethane film.
  • laminated body it is also called a heat seal film.
  • Particle diameter and dispersion coefficient The particle diameter and dispersion coefficient of the aqueous polyester resin dispersion were measured. For the measurement, a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter Counter LS13 320) was used. Then, the particle distribution was prepared on a volume basis by this apparatus, the average diameter and the dispersion coefficient were obtained, and the value of the average diameter was taken as the particle diameter.
  • Crystalline Copolyester Resin (A) Production of Crystalline Copolyester Resin (A-1) 268.3 parts of terephthalic acid and 179.9 parts of isophthalic acid in a reaction vessel equipped with a stirrer, condenser and thermometer 128.7 parts of adipic acid, 27.2 parts of sodium 3,5-dicarbomethoxybenzenesulfonate, 45.6 parts of ethylene glycol, 595.2 parts of 1,4-butanediol, tetra-n-butyl titanate as a catalyst 0.24 parts was charged, and the temperature was raised from 160 ° C. to 240 ° C. over 4 hours to carry out an esterification reaction.
  • the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 260 ° C. Subsequently, the pressure was reduced to 0.3 mmHg or less, and a polycondensation reaction was performed at 260 ° C. for 90 minutes.
  • the number average molecular weight was 15,000, the melting point was 110 ° C., and the acid value was 2.2 KOH mg / g.
  • the number average molecular weight was 13,000, the melting point was 124 ° C., and the acid value was 3.5 KOH mg / g.
  • the obtained crystalline copolymerized polyester resin (A-3) has a molar ratio of terephthalic acid / adipic acid / 3,5-dicarbomethoxybenzene sodium sulfonate // ethylene glycol / 1,4.
  • Crystalline copolyester resins whose compositions are shown in Table 1 in the same manner as in the production example of crystalline copolyester resin (A-1) (A-4) to (A-7) were produced.
  • the measurement results of the resin physical properties are shown in Table 1.
  • Amorphous Copolyester Resin (B) Production of Amorphous Copolyester Resin (B-1) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 244.0 parts of terephthalic acid and 241. 5 parts, sodium 2,5-dicarbomethoxybenzenesulfonate 22.2 parts, ethylene glycol 223.2 parts, neopentyl glycol 249.6 parts, tetra-n-butyl titanate 0.24 parts as a catalyst, 160 The temperature was raised from 4 ° C. to 240 ° C. over 4 hours to carry out the esterification reaction.
  • the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 260 ° C. Subsequently, the pressure was reduced to 0.3 mmHg or less, and a polycondensation reaction was performed at 260 ° C. for 90 minutes.
  • the obtained amorphous copolymerized polyester resin (B-1) was terephthalic acid / isophthalic acid / 3,5-dicarbomethoxybenzene sodium sulfonate // ethylene glycol / neopentyl by molar ratio.
  • Glycol 49 / 48.5 / 2.5 // 50/50.
  • the number average molecular weight was 17,000, the glass transition temperature was 68 ° C., and the acid value was 1.3 KOH mg / g.
  • amorphous copolymer polyester resin (B-2) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 214.1 parts of terephthalic acid, 249.0 parts of isophthalic acid, 3,5-dicarbomethoxybenzenesulfonic acid 62.2 parts of sodium, 223.2 parts of ethylene glycol, 254.4 parts of diethylene glycol, and 0.24 part of tetra-n-butyl titanate as a catalyst were charged and heated from 160 ° C. to 240 ° C. over 4 hours for esterification Reaction was performed. Next, the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 260 ° C.
  • the pressure was reduced to 0.3 mmHg or less, and a polycondensation reaction was performed at 260 ° C. for 90 minutes.
  • the number average molecular weight was 25,000, the glass transition temperature was 45 ° C., and the acid value was 1.8 KOH mg / g.
  • Amorphous Copolyester Resins (B-3) to (B-4) Amorphous copolymers whose compositions are shown in Table 1 in the same manner as in the production of Amorphous Copolyester Resin (B-1) Polymerized polyester resins (B-3) to (B-4) were produced. The measurement results of the resin physical properties are shown in Table 1.
  • the crystalline copolyester resin (A-6) has a high melting point of 166 ° C., which is outside the scope of the claims.
  • the amorphous copolymer polyester resin (B-4) has a low glass transition temperature of 23 ° C., which is outside the scope of the claims.
  • Polyester Resin Aqueous Dispersion Production of Polyester Resin Moisture Dispersion (C-1) Crystalline copolymer polyester resin (A-1) was dispersed in water according to the following procedure.
  • a reaction vessel equipped with a stirrer, a condenser, and a thermometer was charged with 200 parts of a crystalline copolyester resin (A-1) and 150 parts of ethylene glycol monobutyl ether, and the resin was dissolved at 130 ° C. over 1 hour.
  • the mixture was cooled to 70 ° C., 650 parts of water was added, and the mixture was sufficiently stirred to obtain an aqueous polyester resin dispersion (C-1).
  • the particle diameter of the obtained polyester resin aqueous dispersion was 92 nm.
  • polyester resin water-based dispersions (C-2) to (C-7) In the same manner as in the production example of polyester resin aqueous dispersion (C-1), polyester resin water-based dispersions having the composition shown in Table 2 ( C-2) to (C-7) were produced. Table 2 shows the dispersion compositions of the obtained polyester resin aqueous dispersions (C-2) to (C-7).
  • Example of production of aqueous dispersion using amorphous copolymerized polyester resin (B) Production of aqueous dispersion (B-1W) using amorphous copolymerized polyester resin (B) B-1) was dispersed in water according to the following procedure. A reaction vessel equipped with a stirrer, a condenser, and a thermometer was charged with 200 parts of amorphous copolymer polyester resin (B-1), 650 parts of water, and 150 parts of ethylene glycol monobutyl ether, and sufficiently stirred at 80 ° C. for 5 hours. To obtain an aqueous dispersion (B-1W) using an amorphous copolyester resin. The particle size of the obtained aqueous dispersion was 110 nm.
  • Polyester resin aqueous dispersion (D-1) was applied to a 25 ⁇ m thick PET film (E5107 manufactured by Toyobo Co., Ltd.) with a heat seal layer (layer after applying the polyester resin aqueous dispersion and drying). The film was applied to a thickness of 2 ⁇ m, and dried at 120 ° C. for 10 minutes to obtain a heat seal film (H-1) for evaluation.
  • Heat seal films (H-2) to (H-13) were produced in the same manner as the heat seal film (H-1). Each blending ratio is shown in Table 3.
  • Heat seal layers of the heat seal films (H-1) to (H-13) are heat sealed under the conditions of 130 ° C. ⁇ 0.5 seconds ⁇ 40 PSI to form a strip with a width of 15 mm.
  • a test piece was obtained by cutting.
  • the test piece obtained by laminating the heat seal film was peeled between two heat seal films using an autograph (manufactured by Shimadzu Corporation, AG-1kNXplus) (T-peel peel, (Tensile speed 50 mm / min) was measured and used as the initial adhesive strength.
  • the evaluation criteria are as follows, and the evaluation results are shown in Table 4. ⁇ (particularly excellent in practical use): 2.0N or more ⁇ (excellent in practical use): 1.5N or more and less than 2.0N ⁇ (practical): 1.0N or more and less than 1.5N ⁇ (impractical): 1. Less than 0N
  • the heat seal film obtained by the preparation of the heat seal film was cut into 5 cm square, the surface of the heat seal layer was overlaid on the PET film, and the pressure of 10 PSI was applied at 40 ° C. and left for 24 hours. . Subsequently, it cut
  • the crystalline copolyester resin and its aqueous dispersion of the present invention have excellent performance in adhesion, water resistance and boiling water resistance, and are useful as heat seal agents used in food packaging materials and packaging materials for industrial parts. It is.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
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Abstract

La présente invention concerne un agent de thermoscellage qui est utile comme matériel d'emballage des aliments et un matériel d'emballage de produits industriels. L'invention concerne également une résine de copolyester cristallin et une dispersion aqueuse de résine de polyester présentant d'excellentes propriétés de résistance à l'eau et de résistance à l'eau bouillante, lesdites propriétés étant particulièrement problématiques. La résine de copolyester cristallin (A) a un point de fusion compris entre 90 et 130 °C et comprend : un constituant acide polycarboxylique et un constituant polyol utilisé comme constituant copolymère ; une proportion inférieure ou égale à 25 % en mole d'un constituant éthylène glycol utilisé comme constituant polyol ; et une proportion supérieure ou égale à 75 % en mole d'un constituant diol aliphatique linéaire comprenant de 4 à 10 atomes de carbone.
PCT/JP2014/070697 2013-09-30 2014-08-06 Copolyester cristallin, dispersion aqueuse de résine de polyester, et agent de thermoscellage utilisant celle-ci Ceased WO2015045633A1 (fr)

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JP2020084153A (ja) * 2018-11-30 2020-06-04 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
JP2021024110A (ja) * 2019-07-31 2021-02-22 大日本印刷株式会社 積層体および包装体
JP2021075669A (ja) * 2019-11-13 2021-05-20 京セラドキュメントソリューションズ株式会社 インクジェット用インク及びインクジェット用インクの製造方法
JP2021075670A (ja) * 2019-11-13 2021-05-20 京セラドキュメントソリューションズ株式会社 インクジェット用インク及び画像形成方法
WO2021166882A1 (fr) 2020-02-17 2021-08-26 東洋紡株式会社 Résine de polyester cristallin et composition adhésive dans laquelle celle-ci est utilisée
JP2021123671A (ja) * 2020-02-06 2021-08-30 京セラドキュメントソリューションズ株式会社 インクジェット用インク及びインクジェット用インクの製造方法
WO2022202832A1 (fr) 2021-03-25 2022-09-29 東洋紡株式会社 Résine de polyester cristallin et dispersion aqueuse de résine de polyester, et composition pour une utilisation d'adhérence ou de revêtement dans laquelle chacune de ladite résine de polyester cristallin et de la dispersion aqueuse de résine de polyester est utilisée
JP7517628B1 (ja) * 2023-01-26 2024-07-17 東洋紡エムシー株式会社 結晶性ポリエステル樹脂水分散体、塗料組成物、塗膜及び金属缶
WO2024157685A1 (fr) * 2023-01-26 2024-08-02 東洋紡エムシー株式会社 Dispersion aqueuse de résine de polyester cristallin, composition de revêtement, film de revêtement et boîte métallique
JP7598567B1 (ja) * 2023-01-26 2024-12-12 東洋紡エムシー株式会社 結晶性ポリエステル樹脂水分散体、塗料組成物、塗膜及び金属缶
WO2025197145A1 (fr) * 2024-03-22 2025-09-25 東洋紡株式会社 Film stratifié et récipient d'emballage l'utilisant

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JP7139917B2 (ja) 2018-11-30 2022-09-21 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
JP2021024110A (ja) * 2019-07-31 2021-02-22 大日本印刷株式会社 積層体および包装体
JP7395977B2 (ja) 2019-11-13 2023-12-12 京セラドキュメントソリューションズ株式会社 インクジェット用インク及びインクジェット用インクの製造方法
JP2021075669A (ja) * 2019-11-13 2021-05-20 京セラドキュメントソリューションズ株式会社 インクジェット用インク及びインクジェット用インクの製造方法
JP2021075670A (ja) * 2019-11-13 2021-05-20 京セラドキュメントソリューションズ株式会社 インクジェット用インク及び画像形成方法
JP7467890B2 (ja) 2019-11-13 2024-04-16 京セラドキュメントソリューションズ株式会社 インクジェット用インク及び画像形成方法
JP2021123671A (ja) * 2020-02-06 2021-08-30 京セラドキュメントソリューションズ株式会社 インクジェット用インク及びインクジェット用インクの製造方法
JP7447521B2 (ja) 2020-02-06 2024-03-12 京セラドキュメントソリューションズ株式会社 インクジェット用インク及びインクジェット用インクの製造方法
WO2021166882A1 (fr) 2020-02-17 2021-08-26 東洋紡株式会社 Résine de polyester cristallin et composition adhésive dans laquelle celle-ci est utilisée
KR20220139982A (ko) 2020-02-17 2022-10-17 도요보 가부시키가이샤 결정성 폴리에스테르 수지 및 그것을 이용한 접착제 조성물
EP4108457A4 (fr) * 2020-02-17 2024-03-13 TOYOBO MC Corporation Résine de polyester cristallin et composition adhésive dans laquelle celle-ci est utilisée
WO2022202832A1 (fr) 2021-03-25 2022-09-29 東洋紡株式会社 Résine de polyester cristallin et dispersion aqueuse de résine de polyester, et composition pour une utilisation d'adhérence ou de revêtement dans laquelle chacune de ladite résine de polyester cristallin et de la dispersion aqueuse de résine de polyester est utilisée
JP7517628B1 (ja) * 2023-01-26 2024-07-17 東洋紡エムシー株式会社 結晶性ポリエステル樹脂水分散体、塗料組成物、塗膜及び金属缶
WO2024157685A1 (fr) * 2023-01-26 2024-08-02 東洋紡エムシー株式会社 Dispersion aqueuse de résine de polyester cristallin, composition de revêtement, film de revêtement et boîte métallique
JP7598567B1 (ja) * 2023-01-26 2024-12-12 東洋紡エムシー株式会社 結晶性ポリエステル樹脂水分散体、塗料組成物、塗膜及び金属缶
WO2025197145A1 (fr) * 2024-03-22 2025-09-25 東洋紡株式会社 Film stratifié et récipient d'emballage l'utilisant

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