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WO2024172149A1 - Film polyester multicouche - Google Patents

Film polyester multicouche Download PDF

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Publication number
WO2024172149A1
WO2024172149A1 PCT/JP2024/005440 JP2024005440W WO2024172149A1 WO 2024172149 A1 WO2024172149 A1 WO 2024172149A1 JP 2024005440 W JP2024005440 W JP 2024005440W WO 2024172149 A1 WO2024172149 A1 WO 2024172149A1
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WO
WIPO (PCT)
Prior art keywords
polyester film
dicarboxylic acid
mol
acid component
component
Prior art date
Application number
PCT/JP2024/005440
Other languages
English (en)
Japanese (ja)
Inventor
紀志 ▲高▼木
航 三浦
英人 五嶋
裕樹 岡島
良輔 神田
明音 奥永
功 瀧井
Original Assignee
東洋紡株式会社
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 東洋紡株式会社 filed Critical 東洋紡株式会社
Publication of WO2024172149A1 publication Critical patent/WO2024172149A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a laminated polyester film. More specifically, it relates to a laminated polyester film having an easily adhesive coating layer that is optimal for a wide range of applications, including optical applications, packaging applications, and labels.
  • Thermoplastic resin films especially polyester films, have excellent mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, and are therefore widely used in magnetic recording materials, packaging materials, solar cell applications, anti-reflection films used in flat displays, optical films such as diffusion sheets and prism sheets, and films for label printing.
  • polyester films especially polyester films, have excellent mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, and are therefore widely used in magnetic recording materials, packaging materials, solar cell applications, anti-reflection films used in flat displays, optical films such as diffusion sheets and prism sheets, and films for label printing.
  • the adhesion is poor depending on the material used.
  • Patent Document 1 a coating liquid containing a copolymer polyester resin and a urethane resin, or a coating liquid containing a copolymer polyester resin, a urethane resin, and an isocyanate compound, in the coating layer to provide easy adhesion for hard coat processing, prism lens processing, etc.
  • Patent Document 1 a coating liquid containing a copolymer polyester resin and a urethane resin, or a coating liquid containing a copolymer polyester resin, a urethane resin, and an isocyanate compound, in the coating layer to provide easy adhesion for hard coat processing, prism lens processing, etc.
  • UV ink ultraviolet ink
  • Patent Document 2 a technology was known that uses an acrylic copolymer and a polymer having an oxazoline group in the coating layer to provide easy adhesion for label processing.
  • Patent Document 2 a technology was known that uses an acrylic copolymer and a polymer having an oxazoline group in the coating layer to provide easy adhesion for label processing.
  • Patent Document 2 a technology was known that uses an acrylic copolymer and a polymer having an oxazoline group in the coating layer to provide easy adhesion for label processing.
  • Patent Document 2 a technology was known that uses an acrylic copolymer and a polymer having an oxazoline group in the coating layer to provide easy adhesion for label processing.
  • the present invention was made against the background of the problems with the conventional technology. That is, the object of the present invention is to provide a laminated polyester film that has excellent adhesion to a hard coat layer under high temperature and high humidity conditions and excellent adhesion to UV ink.
  • the inventors have investigated the causes of the above problems in order to solve them.
  • the problems of the present invention can be solved when the polyester resin is a laminated polyester film having a coating layer on at least one side of a polyester film substrate, the coating layer being formed from a composition containing a polyester resin, the polyester resin containing a certain amount of a 2,6-naphthalenedicarboxylic acid component and another aromatic dicarboxylic acid component as dicarboxylic acid components, a certain amount or less of an aliphatic dicarboxylic acid component, and a diol component having a specific number of carbon atoms as a diol component. They have further investigated the problem and have completed the present invention.
  • the present invention comprises the following: [1] A laminated polyester film having a coating layer on at least one surface of a polyester film substrate, the coating layer is formed from a composition containing a polyester resin,
  • the polyester resin contains a dicarboxylic acid component and a diol component,
  • the dicarboxylic acid component contains, based on the total dicarboxylic acid components, 30 to 80 mol % of a 2,6-naphthalenedicarboxylic acid component, 20 to 65 mol % of other aromatic dicarboxylic acid components, and 0 to 5 mol % of an aliphatic dicarboxylic acid component;
  • the diol component contains 30 to 80 mol % of a diol component represented by the following formula (1) based on the total diol components: (1) HO-(CH 2 ) n -OH (wherein n is an integer from 5 to 10) Laminated polyester film.
  • aromatic dicarboxylic acid component having a hydrophilic group is an aromatic dicarboxylic acid component having at least one group selected from the group consisting of a sulfo group (-SO 3 H), a carboxyl group (-CO 2 H) and salts thereof.
  • UV ink layer laminated polyester film having an ultraviolet curable ink (UV ink) layer laminated on the coating layer of the laminated polyester film described in any one of [1] to [5].
  • UV ink ultraviolet curable ink
  • a method for producing a laminated polyester film having a coating layer on at least one surface of a polyester film substrate comprising the steps of:
  • the method includes the step of applying a composition (coating liquid) containing a polyester resin to at least one surface of the polyester film substrate,
  • the polyester resin contains a dicarboxylic acid component and a diol component,
  • the dicarboxylic acid component contains, based on the total dicarboxylic acid components, 30 to 80 mol % of a 2,6-naphthalenedicarboxylic acid component, 20 to 65 mol % of other aromatic dicarboxylic acid components, and 0 to 5 mol % of an aliphatic dicarboxylic acid component;
  • the diol component contains 30 to 80 mol % of a diol component represented by the following formula (1) based on the total diol components: (1) HO-(CH 2 ) n -OH (wherein n is an integer from 5 to 10) Manufacturing method.
  • the laminated polyester film of the present invention has excellent adhesion to the hard coat layer under high temperature and high humidity conditions, and excellent adhesion to UV ink.
  • the laminated polyester film of the present invention has a coating layer on at least one side of the polyester film substrate.
  • polyester resin constituting the polyester film substrate examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polytrimethylene terephthalate, etc., as well as copolymerized polyester resins in which a portion of the diol component or dicarboxylic acid component of the above-mentioned polyester resins is replaced with a copolymerization component such as the following.
  • copolymerization component examples include diol components such as diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • diol components such as diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and polyalkylene glycol
  • dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • polyester resins preferably used for the polyester film substrate are mainly selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, etc.
  • polyethylene terephthalate is the most preferable in terms of the balance between physical properties and cost.
  • polyester film substrates made of these polyester resins are preferably biaxially oriented polyester films, which can improve chemical resistance, heat resistance, mechanical strength, etc.
  • the catalyst for polycondensation used in the production of polyester resin is not particularly limited, but antimony trioxide is preferable because it is inexpensive and has excellent catalytic activity. It is also preferable to use a germanium compound or a titanium compound. Further preferable polycondensation catalysts include catalysts containing aluminum and/or its compound and a phenolic compound, catalysts containing aluminum and/or its compound and a phosphorus compound, and catalysts containing an aluminum salt of a phosphorus compound.
  • the polyester film substrate is not particularly limited in terms of its layer structure. It may be a single-layer polyester film, or it may be a two-layer structure with different components, or it may be a polyester film substrate consisting of at least three layers, including an outer layer and an inner layer.
  • the laminated polyester film of the present invention has a coating layer formed of a composition containing a polyester resin laminated on at least one side of the polyester film substrate.
  • the coating layer may be provided on both sides of the polyester film, or may be provided on only one side of the polyester film, with a coating layer of a different resin being provided on the other side.
  • the polyester resin used for forming the coating layer comprises a dicarboxylic acid component and a diol component.
  • the dicarboxylic acid component contains, based on the total dicarboxylic acid components, 0 to 5 mol % of an aliphatic dicarboxylic acid component, 30 to 80 mol % of a 2,6-naphthalenedicarboxylic acid component, and 20 to 65 mol % or more of other aromatic dicarboxylic acid components.
  • the diol component contains, based on the total diol components, 30 to 80 mol % of a diol represented by the following formula (1): (1) HO-(CH 2 ) n -OH (wherein n is an integer from 5 to 10)
  • the ester group concentration of the polyester resin is preferably 8000 eq/10 6 g or less.
  • the lower limit of the proportion of 2,6-naphthalenedicarboxylic acid component in the dicarboxylic acid component is 30 mol%, preferably 40 mol%, and more preferably 45 mol%. A proportion of 30 mol% or more is preferable because it improves solvent resistance and adhesion to the hard coat.
  • the upper limit of the proportion of 2,6-naphthalenedicarboxylic acid component as a dicarboxylic acid component is 80 mol%, preferably 70 mol%, and more preferably 60 mol%.
  • a proportion of 60 mol% or less is preferable because it can improve adhesion to ink, improve water dispersibility when dispersing polyester resin in water to form an aqueous coating liquid, and further suppress coating film cracking during the stretching process in in-line coating that is normally used when forming a coating layer.
  • aliphatic dicarboxylic acid components examples include adipic acid and sebacic acid.
  • the proportion of aliphatic dicarboxylic acid components in the dicarboxylic acid components is adjusted in the range of 0 to 5 mol%. The lower this proportion, the better. It is preferably less than 5 mol%, and more preferably 3 mol% or less. This is preferable because it improves the hydrolysis resistance of the coating film under high temperature and high humidity conditions and improves adhesion to the hard coat.
  • aromatic dicarboxylic acid components include, for example, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, etc. Among these, isophthalic acid and terephthalic acid are preferred.
  • the lower limit of the proportion of the other aromatic dicarboxylic acid component in the dicarboxylic acid component is 20 mol%, preferably 30 mol%, and more preferably 40 mol%. A proportion of 20 mol% or more is preferable because it improves solvent resistance and adhesion to the hard coat.
  • the upper limit of the proportion of the other aromatic dicarboxylic acid component is 65 mol%, preferably 50 mol%. A proportion of 65 mol% or less is preferable because it improves the flexibility of the coating film and improves adhesion to the ink.
  • the lower limit of the proportion of the diol component represented by formula (1) in the diol component is preferably 30 mol%, more preferably 40 mol%, and even more preferably 50 mol%. A proportion of 30 mol% or more is preferable because it improves the flexibility of the coating film and improves the ink adhesion.
  • the upper limit of the proportion of the diol represented by formula (1) is preferably 80 mol%, more preferably 75 mol%. A proportion of 80 mol% or less is preferable because it improves the water dispersibility when the polyester resin is dispersed in water to form an aqueous coating liquid.
  • the diol component may contain a diol component represented by the following formula (2).
  • the upper limit of the proportion of the diol component is preferably 20 mol%, more preferably 15 mol%, further preferably 10 mol%, and particularly preferably 5 mol%.
  • the lower limit is 0 mol%.
  • a ratio of 20 mol % or less is preferred because it improves the solubility in the hard coat solvent and improves the adhesion to the hard coat, and further improves the flexibility of the coating film and improves the adhesion to the ink.
  • the diol component may contain other diol components in addition to the diol components represented by formula (1) and formula (2).
  • examples of such other diol components include polyalkylene glycols such as diethylene glycol; alkylene glycols having 3 to 10 carbon atoms and a branched structure such as neopentyl glycol and 2-butyl-2-ethyl-1,3-propanediol; and the like.
  • the upper limit of the ester group concentration of the polyester resin used for forming the coating layer is preferably 8000eq/ 106g , more preferably 7800eq/ 106g , and even more preferably 7500eq/ 106g . If it is 8000eq/ 106g or less, the hydrolysis resistance of the coating film under high temperature and high humidity can be improved, and the adhesion to the hard coat can be improved, which is preferable.
  • the lower limit of the ester group concentration is preferably 5000eq/ 106g , and if it is 5000eq/ 106g or more, the toughness of the resin can be improved, which is preferable.
  • the ester group concentration can be calculated by the method described in the examples described later.
  • the coating layer is formed by applying a composition (coating liquid) containing a polyester resin to at least one side of a polyester film substrate.
  • the coating liquid is a liquid medium in which a polyester resin is dissolved or dispersed.
  • liquid media include water, organic solvents (e.g., water-soluble organic solvents such as alcohols, alkyl cellosolves, ketone-based solvents, and ether-based solvents; water-insoluble organic solvents such as toluene and ethyl acetate), and mixed solvents thereof.
  • a mixed solvent (aqueous solution) of water and a water-soluble organic solvent is preferable.
  • the coating liquid is preferably an aqueous coating liquid, and examples of the aqueous coating liquid include an aqueous coating liquid in which a polyester resin is dispersed or dissolved in an aqueous solution containing less than 50 mass% of a water-soluble organic solvent (isopropanol, etc.).
  • a water-soluble organic solvent isopropanol, etc.
  • polyester resin When the polyester resin is used as a water-based coating liquid, it is preferable to use a water-soluble or water-dispersible polyester resin.
  • water-soluble or water-dispersible polyester resins include copolymers containing a copolymer component (e.g., an aromatic dicarboxylic acid component, etc.) having a hydrophilic functional group (hydrophilic group).
  • hydrophilic group examples include a sulfo group (-SO 3 H), a carboxyl group (-CO 2 H), and groups consisting of salts thereof.
  • Examples of the copolymer component having a hydrophilic group include an aromatic dicarboxylic acid component having a hydrophilic group, and specific examples thereof include sulfoterephthalic acid (5-sulfoterephthalic acid, etc.), sulfoisophthalic acid (5-sulfoisophthalic acid, etc.), and salts thereof (5-sodium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, etc.).
  • the ratio of aromatic dicarboxylic acid components having hydrophilic groups in the dicarboxylic acid components can be adjusted in the range of 0 to 10 mol%, preferably 1 to 9 mol%, and more preferably 1 to 8 mol%. This allows the polyester resin to be suitably dispersed or dissolved in the aqueous solution.
  • the laminated polyester film of the present invention may contain a crosslinking agent as a component other than the polyester resin in the composition (coating solution) for forming the coating layer.
  • a crosslinking agent an isocyanate compound, particularly a blocked isocyanate compound, is preferred.
  • the lower limit of the boiling point of the blocking agent contained in the blocked isocyanate compound is preferably 150°C, more preferably 160°C, even more preferably 180°C, particularly preferably 200°C, and most preferably 210°C.
  • the higher the boiling point of the blocking agent the more the blocking agent is suppressed from volatilizing even during the drying process after application of the coating liquid or during the heat addition during the film formation process in the case of the in-line coating method, the less the occurrence of minute unevenness on the coating surface is suppressed, and the transparency of the film is improved.
  • the upper limit of the boiling point of the blocking agent is not particularly limited, but it is thought that the upper limit is about 300°C from the viewpoint of productivity.
  • the boiling point is related to the molecular weight
  • the molecular weight of the blocking agent is preferably 50 or more, more preferably 60 or more, and even more preferably 80 or more.
  • the upper limit of the dissociation temperature of the blocking agent from the blocked isocyanate compound is preferably 200°C, more preferably 180°C, even more preferably 160°C, particularly preferably 150°C, and most preferably 120°C.
  • the blocking agent dissociates from the blocked isocyanate compound due to the heat addition in the film formation process, and a functional group (isocyanate group) is regenerated. This crosslinks with the polyester resin, improving the adhesion to the polyester film substrate.
  • the dissociation temperature of the blocked isocyanate compound is below the above temperature, the dissociation of the blocking agent proceeds sufficiently, resulting in good adhesion, especially good resistance to moist heat.
  • the blocking agent used in the blocked isocyanate compound is preferably one having a dissociation temperature of 120°C or less and a boiling point of 150°C or more, and examples thereof include bisulfite compounds (sodium bisulfite, etc.); pyrazole compounds (3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, etc.); active methylene compounds (malonic acid diesters such as dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.); ketone compounds (methyl ethyl ketone, etc.); triazole compounds (1,2,4-triazole, etc.). Among these, pyrazole compounds are preferred from the standpoint of resistance to moist heat and yellowing.
  • the precursor of the blocked isocyanate compound is preferably a polyisocyanate compound having three or more functionalities (having three or more isocyanate groups).
  • the polyisocyanate compound having three or more functionalities can be easily obtained from a diisocyanate monomer having two isocyanate groups.
  • a biuret, a nurate, an adduct, etc. obtained by modifying a diisocyanate monomer (e.g., an aromatic diisocyanate, an aliphatic diisocyanate, an araliphatic diisocyanate, an alicyclic diisocyanate, etc.) can be mentioned.
  • the biuret form is a self-condensation product having a biuret bond formed by self-condensation of a diisocyanate monomer, and an example thereof is a biuret form of hexamethylene diisocyanate.
  • the nurate form is a trimer of a diisocyanate monomer, and examples thereof include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, and a trimer of tolylene diisocyanate.
  • the adduct refers to a tri- or higher functional isocyanate compound obtained by reacting a diisocyanate monomer with a tri- or higher functional low-molecular-weight active hydrogen-containing compound
  • examples of such an adduct include a compound obtained by reacting trimethylolpropane with hexamethylene diisocyanate, a compound obtained by reacting trimethylolpropane with tolylene diisocyanate, a compound obtained by reacting trimethylolpropane with xylylene diisocyanate, and a compound obtained by reacting trimethylolpropane with isophorone diisocyanate.
  • the diisocyanate monomers include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, phenylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, and 2,2'-diphenylpropane-4,4'-diisocyanate.
  • aromatic diisocyanates such as 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; aromatic aliphatic diisocyanates such as xylylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane; aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc. In terms of transparency, adhesion, and resistance to moist heat, aliphatic and alicyclic diisocyanates and their modified products are preferred, and are suitable for optical applications that require no yellowing and high transparency.
  • a blocked isocyanate compound can introduce a hydrophilic group into a polyisocyanate compound, which is a precursor, to impart water solubility or water dispersibility.
  • hydrophilic groups include (1) quaternary ammonium salts of dialkylamino alcohols and quaternary ammonium salts of dialkylaminoalkylamines, (2) sulfonates, carboxylates, and phosphates, and (3) polyethylene glycols and polypropylene glycols with one end blocked with an alkyl group.
  • the polymer becomes (1) cationic, (2) anionic, or (3) nonionic.
  • anionic and nonionic polymers are preferred because they are easily compatible with other water-soluble resins, as most other water-soluble resins are anionic.
  • anionic polymers have excellent compatibility with other resins, and nonionic polymers do not have ionic hydrophilic groups, so they are also preferred for improving resistance to moist heat.
  • anionic hydrophilic groups those having hydroxyl groups for introduction into polyisocyanates and carboxylic acid groups for imparting hydrophilicity are preferred.
  • examples include glycolic acid, lactic acid, tartaric acid, citric acid, oxybutyric acid, oxyvaleric acid, hydroxypivalic acid, dimethylolacetic acid, dimethylolpropanoic acid, dimethylolbutanoic acid, and polycaprolactones having carboxylic acid groups.
  • organic amine compounds are preferred.
  • Examples include linear, branched primary, secondary or tertiary amines having 1 to 20 carbon atoms, such as ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, 2-ethylhexylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine and ethylenediamine; cyclic amines, such as morpholine, N-alkylmorpholine and pyridine; and hydroxyl group-containing amines, such as monoisopropanolamine, methylethanolamine, methylisopropanolamine, dimethylethanolamine, diisopropanolamine, diethanolamine, triethanolamine, diethylethanolamine and triethanolamine.
  • the repeating units of ethylene oxide and/or propylene oxide of polyethylene glycol and polypropylene glycol capped at one end with an alkyl group are preferably 3 to 50, more preferably 5 to 30. If the repeating units are small, the compatibility with the resin will be poor and the haze will increase, and if the repeating units are large, the adhesion under high temperature and high humidity may decrease.
  • nonionic, anionic, cationic, or amphoteric surfactants can be added to the blocked isocyanate of the present invention.
  • surfactants such as polyethylene glycol, polyhydric alcohol fatty acid esters, etc., anionic fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, sulfosuccinates, alkyl phosphates, etc., cationic alkylamine salts, alkylbetaines, etc., carboxylate amine salts, sulfonate amine salts, and sulfate ester salts can be mentioned.
  • water-soluble organic solvents can also be included.
  • the organic solvent used in the reaction can be removed and another organic solvent can be added.
  • the lower limit of the crosslinking agent content is preferably 5% by mass, more preferably 7% by mass, even more preferably 10% by mass, and most preferably 12% by mass. If it is 5% by mass or more, blocking resistance can be improved, which is preferable.
  • the upper limit of the crosslinking agent content is preferably 50% by mass, more preferably 40% by mass, even more preferably 35% by mass, and most preferably 30% by mass. If it is 50% by mass or less, transparency will be high, which is preferable.
  • the coating layer in the present invention may contain known additives, such as surfactants, antioxidants, heat stabilizers, weather stabilizers, UV absorbers, organic lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, etc., within the range that does not impair the effects of the present invention.
  • additives can be contained in the composition (coating liquid) for forming the coating layer.
  • particles to be included in the coating layer in the present invention include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, and mixtures thereof, as well as other general inorganic particles such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, and other inorganic particles used in combination, and organic polymer particles such as styrene-based, acrylic-based, melamine-based, benzoguanamine-based, and silicone-based particles.
  • the average particle size of the particles in the coating layer is preferably 0.04 to 2.0 ⁇ m, and more preferably 0.1 to 1.0 ⁇ m. If the average particle size of the particles is 0.04 ⁇ m or more, it becomes easier to form irregularities on the film surface, improving the handling properties such as the slipperiness and winding properties of the film, and it is preferable because the processability during lamination is good. On the other hand, if the average particle size of the particles is 2.0 ⁇ m or less, it is preferable because the particles are less likely to fall off.
  • the particle concentration in the coating layer is preferably 1 to 20 mass% of the solid components.
  • the average particle size was measured by observing the particles on the cross section of the laminated polyester film with a scanning electron microscope, observing 30 particles, and taking the average value as the average particle size.
  • the particle size of irregular particles can be calculated as the equivalent circle diameter.
  • the equivalent circle diameter is calculated by dividing the observed particle area by ⁇ , calculating the square root, and multiplying it by two.
  • the PET resin is thoroughly vacuum dried, it is fed to an extruder, and the molten PET resin at about 280°C is melt-extruded from a T-die onto a rotating cooling roll in the form of a sheet, and then cooled and solidified using an electrostatic application method to obtain an unstretched PET sheet.
  • the unstretched PET sheet may be of single layer construction, or may be of multilayer construction using a co-extrusion method.
  • the resulting unstretched PET sheet is uniaxially or biaxially stretched to achieve crystal orientation.
  • the sheet is stretched 2.5 to 5.0 times in the longitudinal direction using rolls heated to 80 to 120°C to obtain a uniaxially stretched PET film, and the ends of the film are then held with clips and guided to a hot air zone heated to 80 to 180°C where it is stretched 2.5 to 5.0 times in the width direction.
  • uniaxial stretching the sheet is stretched 2.5 to 5.0 times in a tenter. After stretching, the sheet is then guided to a heat treatment zone where it is heat treated to complete the crystal orientation.
  • the lower limit of the temperature in the heat treatment zone is preferably 170°C, more preferably 180°C. If the temperature in the heat treatment zone is 170°C or higher, curing is sufficient, and blocking properties in the presence of liquid water are good, which is preferable, and there is no need to extend the drying time.
  • the upper limit of the temperature in the heat treatment zone is preferably 230°C, more preferably 200°C. If the temperature in the heat treatment zone is 230°C or lower, there is no risk of the physical properties of the film decreasing, which is preferable.
  • the coating layer can be provided after the film is manufactured or during the manufacturing process. From the viewpoint of productivity, it is particularly preferable to form a coating layer by applying a coating liquid to at least one side of the PET film at any stage of the film manufacturing process, i.e., unstretched or uniaxially stretched PET film.
  • any known method can be used to apply this coating liquid to the PET film. Examples include reverse roll coating, gravure coating, kiss coating, die coater, roll brush, spray coating, air knife coating, wire bar coating, pipe doctor, impregnation coating, curtain coating, etc. These methods can be used alone or in combination.
  • the thickness of the coating layer can be set appropriately in the range of 0.001 to 2.00 ⁇ m, but in order to achieve both processability and adhesiveness, a range of 0.01 to 1.00 ⁇ m is preferable, more preferably 0.02 to 0.80 ⁇ m, and even more preferably 0.05 to 0.50 ⁇ m. If the thickness of the coating layer is 0.001 ⁇ m or more, good adhesiveness is obtained, which is preferable. If the thickness of the coating layer is 2.00 ⁇ m or less, blocking is less likely to occur, which is preferable.
  • the upper limit of the haze of the laminated polyester film of the present invention is preferably 1.5%, more preferably 1.3%, even more preferably 1.2%, and particularly preferably 1.0%.
  • a haze of 1.5% or less is preferable in terms of transparency, and the film can be suitably used in optical films where transparency is required.
  • the lower the haze, the better, and ideally 0% is most preferable, but a haze of 0.1% or more is acceptable, and even 0.3% or more will not cause any practical problems.
  • ester group concentration was calculated as the reciprocal of the average molecular weight of units formed from each acid component and each glycol component multiplied by 2 ⁇ 10 6.
  • the average molecular weight of the formed units is 298 g/mol, so the ester group concentration is calculated to be 6704 eq/10 6 g.
  • UV ink manufactured by T&K TOKA Co., Ltd., product name "BEST CURE UV161 Indigo S”
  • a printing machine manufactured by Akebono Seisakusho Co., Ltd., product name "RI Tester”
  • the film coated with the ink layer was irradiated with 40 mJ/ cm2 of ultraviolet light using a high-pressure mercury lamp to cure the ultraviolet-curable ink.
  • a cutter guide with a gap of 2 mm, 100 grid-shaped cuts were made on the ink layer surface, penetrating the ink layer and reaching the film substrate.
  • cellophane adhesive tape manufactured by Nichiban, No. 405; 24 mm wide
  • a coating solution for forming a hard coat layer having the following composition was applied onto the coating layer of the laminated polyester film using a #5 wire bar, and the solution was dried for 1 minute at 80° C. to remove the solvent.
  • the film coated with the hard coat layer was irradiated with ultraviolet light of 200 mJ/cm 2 using a high pressure mercury lamp to obtain a hard coat film.
  • Methyl ethyl ketone 36.00% by mass Toluene 18.00% by mass Cyclohexanone 6.00% by mass Urethane acrylate 40.00% by mass (BS577, manufactured by Arakawa Chemical Industries, Ltd.)
  • Surfactant 0.10% by mass Photopolymerization initiator 2.00% by mass (Irgacure 184, manufactured by Chiba Specialty Chemicals)
  • the hard coat film thus prepared was left in a high-temperature, high-humidity chamber under an environment of 85°C and 85% RH for 240 hours.
  • a cutter guide with a gap of 2 mm was used to make 100 grid-shaped cuts on the hard coat layer surface, penetrating the hard coat layer and reaching the film substrate.
  • a cellophane adhesive tape manufactured by Nichiban, No. 405; 24 mm wide was attached to the grid-shaped cut surface, and rubbed with an eraser to completely adhere it.
  • the cellophane adhesive tape was peeled vertically from the hard coat layer surface of the hard coat laminated film, and the number of squares peeled off from the hard coat layer surface of the hard coat laminated film was counted visually, and the adhesion between the hard coat layer and the film substrate was calculated from the following formula.
  • the squares that were partially peeled off were also counted as peeled squares.
  • the hard coat adhesion was considered to be acceptable at 90(%).
  • Hard coat adhesion (%) 100 - (number of peeled squares)
  • polyester resin (A-1).
  • the resulting polyester resin had a reduced viscosity of 0.52 dl/g, a glass transition temperature (Tg) of 32° C., and an acid value of 20 eq/t.
  • Polyester resins (A-2) to (A-15) having different compositions were obtained in a similar manner.
  • the compositions of these copolymer polyester resins were measured by 1 H-NMR, and the results are shown in Table 1.
  • Example 1 (1) Preparation of Coating Solution A coating solution was prepared by mixing the following coating agent with a mixed solvent of water and isopropanol. Polyester water dispersion (Aw-1) 20.05 parts by weight Particles 0.47 parts by weight (dry process silica with an average particle size of 200 nm, solid content concentration 3.5% by weight) Particles: 1.85 parts by mass (silica sol with an average particle size of 40 to 50 nm, solid content concentration of 30% by mass) Surfactant: 0.30 parts by weight (silicone-based, solid content concentration: 10% by weight)
  • the pellets were fed to an extruder, melt-extruded into a sheet at about 280° C., and rapidly cooled and solidified on a rotating cooling metal roll maintained at a surface temperature of 20° C. to obtain an unstretched PET sheet.
  • This unstretched PET sheet was heated to 100°C using a group of heated rolls and an infrared heater, and then stretched 3.5 times in the longitudinal direction using a group of rolls with different peripheral speeds to obtain a uniaxially stretched PET film.
  • the coating solution that had been left at room temperature for 5 hours or more was applied to one side of a PET film by roll coating, and then dried at 80° C. for 20 seconds.
  • the coating amount after the final (biaxial stretching) drying was adjusted to 0.10 g/m 2 (coating layer thickness after drying: 100 nm).
  • the film was then stretched 4.0 times in the width direction at 120° C. using a tenter, heated at 230° C. for 5 seconds while the length of the film in the width direction was fixed, and further subjected to a 3% width direction relaxation treatment at 100° C. for 10 seconds to obtain a 100 ⁇ m laminated polyester film.
  • the evaluation results are shown in Table 2.
  • Example 2 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-2).
  • Example 3 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-3).
  • Example 4 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-4).
  • Example 5 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-5).
  • Example 6 A laminated polyester film was obtained in the same manner as in Example 1, except that the following coating agent was mixed into a mixed solvent of water and isopropanol.
  • Polyester water dispersion (Aw-4) 15.00 parts by weight
  • Crosslinking agent (B-1) 3.00 parts by weight
  • Particles 0.47 parts by weight dry process silica with an average particle size of 200 nm, solid content concentration 3.5% by weight
  • Particles 1.85 parts by mass (silica sol with an average particle size of 40 to 50 nm, solid content concentration of 30% by mass)
  • Surfactant 0.30 parts by weight (silicone-based, solid content concentration: 10% by weight)
  • Example 7 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-14).
  • Example 8 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-15).
  • the coating layer formed on at least one surface of the polyester film substrate contained a polyester resin containing an excessive amount of 2,6-naphthalenedicarboxylic acid component in a dicarboxylic acid component, and therefore the flexibility of the coating film was reduced and the adhesion to UV ink was not satisfactory.
  • the coating layer formed on at least one side of the polyester film substrate contained a polyester resin that did not contain a sufficient amount of 2,6-naphthalenedicarboxylic acid component in the dicarboxylic acid component, resulting in reduced solvent resistance and unsatisfactory adhesion to the hard coat.
  • Example 4 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-9).
  • Example 5 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-10).
  • the coating layer formed on at least one side of the polyester film substrate contained a polyester resin containing an excessive amount of an aliphatic carboxylic acid component in a dicarboxylic acid component, and therefore the adhesion to the hard coat under high temperature and high humidity conditions was not satisfactory.
  • Example 7 A laminated polyester film was obtained in the same manner as in Example 1, except that the polyester water dispersion was changed to (Aw-12).
  • the coating layer formed on at least one side of the polyester film substrate contained a polyester resin that did not contain a sufficient amount of the diol component represented by formula (1) in the diol component, and therefore the adhesion to UV ink was not satisfactory.
  • the coating layer formed on at least one side of the polyester film substrate contained a polyester resin that did not contain the diol component represented by formula (1) in the diol component, and therefore did not have satisfactory adhesion to the hard coat layer under high temperature and high humidity conditions.
  • Tables 1 and 2 summarize the evaluation results for each example and comparative example.
  • the present invention makes it possible to provide a laminated polyester film that can be used effectively in a wide range of fields, including optical applications, packaging applications, and label applications.

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

Abstract

La présente invention vise à fournir un film polyester multicouche qui présente une excellente adhérence à une couche de revêtement dur dans des environnements à haute température et à forte humidité et une excellente adhérence à une encre UV. A cet effet, la présente invention concerne un film polyester multicouche ayant une couche de revêtement sur au moins une surface d'un substrat de film polyester. La couche de revêtement est formée à partir d'une composition contenant une résine polyester. La résine polyester contient un composant d'acide dicarboxylique et un composant diol. Le composant d'acide dicarboxylique contient de 30 à 80 % en moles d'un composant d'acide 2,6-naphtalènedicarboxylique, de 20 à 65 % en moles d'un autre composant d'acide dicarboxylique aromatique et de 0 à 5 % en moles d'un composant d'acide dicarboxylique aliphatique par rapport à tous les composants d'acide dicarboxylique. Le composant diol contient de 30 à 80 % en moles d'un composant diol représenté par la formule (1) par rapport à tous les composants diol.　Formule (1) : HO-(CH2)n-OH (dans la formule, n est un nombre entier entre 5 et 10).
PCT/JP2024/005440 2023-02-17 2024-02-16 Film polyester multicouche WO2024172149A1 (fr)

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JP2023-023801 2023-02-17

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012250498A (ja) * 2011-06-06 2012-12-20 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
JP2014065887A (ja) * 2012-09-10 2014-04-17 Toyobo Co Ltd 光学用易接着性ポリエステルフィルム
JP2014124868A (ja) * 2012-12-27 2014-07-07 Teijin Dupont Films Japan Ltd 積層ポリエステルフィルム
JP2017109489A (ja) * 2015-12-14 2017-06-22 ユニチカ株式会社 積層フィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012250498A (ja) * 2011-06-06 2012-12-20 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
JP2014065887A (ja) * 2012-09-10 2014-04-17 Toyobo Co Ltd 光学用易接着性ポリエステルフィルム
JP2014124868A (ja) * 2012-12-27 2014-07-07 Teijin Dupont Films Japan Ltd 積層ポリエステルフィルム
JP2017109489A (ja) * 2015-12-14 2017-06-22 ユニチカ株式会社 積層フィルム

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