WO2021256224A1 - Film de polyester multicouche - Google Patents

Film de polyester multicouche Download PDF

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Publication number
WO2021256224A1
WO2021256224A1 PCT/JP2021/020518 JP2021020518W WO2021256224A1 WO 2021256224 A1 WO2021256224 A1 WO 2021256224A1 JP 2021020518 W JP2021020518 W JP 2021020518W WO 2021256224 A1 WO2021256224 A1 WO 2021256224A1
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WIPO (PCT)
Prior art keywords
mass
parts
water
blocked isocyanate
acid
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PCT/JP2021/020518
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English (en)
Japanese (ja)
Inventor
博 多喜
紀志 ▲高▼木
功 瀧井
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to CN202180037538.8A priority Critical patent/CN115697706A/zh
Priority to KR1020227035605A priority patent/KR20230029591A/ko
Priority to JP2021545794A priority patent/JPWO2021256224A1/ja
Publication of WO2021256224A1 publication Critical patent/WO2021256224A1/fr

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    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a laminated polyester film. More specifically, the present invention relates to a laminated polyester film having easy adhesiveness, which is most suitable for all fields such as optics, packaging, and labels having a coating layer having excellent transparency (low haze), durability, and few coating film defects.
  • Thermoplastic resin films especially polyester films, have excellent mechanical properties, electrical properties, dimensional stability, transparency, chemical resistance, etc., and therefore have excellent properties such as magnetic recording materials, packaging materials, solar cell applications, and flat displays. It is widely used in antireflection films, diffusion sheets, optical films such as prism sheets, and label printing films. However, since the surface of the polyester film is highly crystallinely oriented, it has a drawback of poor adhesion to various paints, resins, and inks in processing for these applications.
  • a nonionic or anionic hydrophilic group is introduced into the skeleton in order to develop water dispersibility in the cross-linking agent itself. If the amount of this hydrophilic group introduced is low, the water dispersibility of the cross-linking agent itself is lowered, and as a result, the storage stability of the coating material is deteriorated. Further, when the amount of the hydrophilic group introduced is increased, the amount of blocked isocyanate in the cross-linking agent is relatively reduced, so that the performance such as durability of the coating film is insufficient.
  • These core-shell structure emulsions improve the dispersion stability of the coating liquid, and when applied to a polyester film substrate or the like and sufficiently cured, good adhesion is exhibited, but when the curing is insufficient. It was found that the coating film had a peeling defect due to contact with a traveling roll or the like.
  • a tension control roll is often provided in order to suppress tension fluctuations in the stretching process such as in the width direction after coating and drying. There is a tendency for the coating layer to have frequent peeling defects.
  • the present invention is intended to solve the above-mentioned problems of the polyester film, and is used for optics and packaging, which has a coating layer having excellent transparency (low haze), excellent durability, and few coating film defects. It is intended to provide a laminated polyester film having optimum easy adhesiveness for all fields such as for labels.
  • the present invention has the following configuration.
  • 1. It has a coating film formed from a coating liquid containing an aqueous dispersion of a hydrophobic block isocyanate compound hydrophilized by an anionic emulsifier, a water-dispersible polyurethane resin having a carboxyl group, and a water-dispersible polyester resin. Laminated polyester film with less than 5.0 pieces / m 2 of peeling defects.
  • 2. The laminated polyester film according to the first item above, wherein the anionic emulsifier that hydrophilizes the aqueous dispersion of the hydrophobic blocked isocyanate compound is an aqueous dispersible polyurethane resin having a carboxyl group.
  • 3. The laminated polyester film according to the first or second above, which has a core-shell structure having a hydrophobic blocked isocyanate compound as a core and a water-dispersible polyurethane resin having a carboxyl group as a shell.
  • the laminated polyester film of the present invention is excellent in adhesiveness to ultraviolet (UV) curable resins such as a hard coat layer, a lens layer, and ink, but is particularly excellent in adhesiveness to a high level of UV ink.
  • UV ultraviolet
  • the polyester resin constituting the polyester film base material includes polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polytrimethylene terephthalate and the like, as well as the diol component or dicarboxylic acid component of the polyester resin as described above. It is a copolymerized polyester resin in which a part of the above is replaced with the following copolymerization component.
  • a diol component such as diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, polyalkylene glycol, etc.
  • the polyester resin suitably used for the polyester film substrate in the present invention is mainly selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate.
  • polyethylene terephthalate is most preferable from the viewpoint of the balance between physical properties and cost.
  • the polyester film base material composed of these polyester resins is preferably a biaxially stretched polyester film, and can improve chemical resistance, heat resistance, mechanical strength and the like.
  • the catalyst for polycondensation used in the production of polyester resin is not particularly limited, but antimony trioxide is suitable because it is an inexpensive catalyst 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 compounds and phenolic compounds, catalysts containing aluminum and / or its compounds and phosphorus compounds, and catalysts containing aluminum salts of phosphorus compounds.
  • the polyester film base material in the present invention is not particularly limited in its layer structure, and may be a single-layer polyester film or a two-layer structure having different components from each other, and the outer layer and the inner layer may be formed. It may be a polyester film base material having at least three layers.
  • the laminated polyester film of the present invention is made of a hydrophobic blocked isocyanate compound, a water-dispersible polyurethane resin having a carboxyl group, and a water-dispersible polyester resin in order to improve the adhesiveness to a hard coat layer, a lens layer, an ink and the like. It is preferable that the formed coating layers are laminated.
  • 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, and a different type of resin coating layer may be provided on the other side.
  • the coating layer of the present invention is preferably formed mainly from a hydrophobic block isocyanate compound hydrolyzed by an anionic emulsifier, a water-dispersible polyurethane resin having a carboxyl group, and a water-dispersible polyester resin, but the hydrophobic block.
  • the anionic emulsifier that hydrophilizes the isocyanate compound is preferably an water-dispersible polyurethane resin having a carboxyl group, and as a particularly desirable form, a hydrophobic blocked isocyanate compound and a water-dispersible polyurethane resin having a carboxyl group are hydrophobic.
  • a core-shell structure having a blocked isocyanate compound as a core and a water-dispersible polyurethane resin having a carboxyl group as a shell It is preferable to have a core-shell structure having a blocked isocyanate compound as a core and a water-dispersible polyurethane resin having a carboxyl group as a shell.
  • the above-mentioned hydrophilization does not mean only complete hydrophilization, but can be said to achieve the purpose if water dispersibility is provided so that an aqueous coating liquid can be prepared.
  • the water-dispersible polyurethane resin having a hydrophobic blocked isocyanate compound and a carboxyl group preferably has a mass ratio in the range of 5/95 to 80/20, more preferably 10/90 to 70/30, and further 20 /. The range of 80 to 60/40 is preferable.
  • the hydrophobic blocked isocyanate compound is 5 parts by mass or more because durability such as moisture resistance is improved.
  • the total of the hydrophobic block isocyanate compound and the water-dispersible polyurethane resin having a carboxyl group is 100 parts by mass, if the water-dispersible polyurethane resin having a carboxyl group is 20 parts by mass or more, the stability of the coating liquid with time is determined. It is preferable because the transparency (low haze) and the adhesiveness to the hard coat layer, the lens layer, the ink and the like are improved. Further, the total of the above-mentioned hydrophobic block isocyanate compound and the water-dispersible polyurethane resin having a carboxyl group and the polyester resin are preferably in the range of 10/90 to 90/10 as a mass ratio, and more preferably 20/80 to 80/.
  • the hydrophobic blocked isocyanate compound and the water-dispersible polyurethane resin having a carboxyl group and the total of the polyester resin are 100 parts by mass, the hydrophobic blocked isocyanate compound and the water-dispersible polyurethane resin having a carboxyl group
  • the total amount is 10 parts by mass or more, the adhesiveness to the hard coat layer, the lens layer, the ink and the like is improved, which is preferable.
  • the polyester resin is 10 parts by mass or more, it is preferable that the peeling defect of the coating film is easily suppressed.
  • the peeling defect is preferably less than 5.0 pieces / m 2 , more preferably less than 4.0 pieces / m 2 , and further preferably less than 3.0 pieces / m 2. be.
  • the peeling defect is less than 5.0 pieces / m 2 , the yield of the accepted product due to the peeling defect becomes a satisfactory level, which is preferable, especially in optical applications.
  • an aqueous dispersion of a hydrophobic blocked isocyanate compound in which the coating film is hydrophilized by an anionic emulsifier, an aqueous dispersion polyurethane resin having a carboxyl group, and water It is preferably formed from a coating liquid containing a dispersible polyester resin, and more preferably the ratio of the compound, the resin and the compound as described above.
  • the defect of peeling is most preferably 0 pieces / m 2 , but 0.5 pieces / m 2 or more may be used.
  • each composition of the coating layer will be described in detail.
  • hydrophobic blocked isocyanate compound In the present invention, a hydrophobic blocked isocyanate compound is used. Hydrophobicity means that no hydrophilic group is introduced into the molecule of the blocked isocyanate compound so as to allow self-emulsification or water dispersion of the compound alone. Examples of these hydrophilic groups include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a polyoxyethylene group and the like. However, the presence of a small amount of hydrophilic groups is not excluded when the compound is introduced for the purpose of adjusting the physical characteristics of the compound or when it is derived from the synthetic reaction residue of the compound or the impurities of the raw material. In the present invention, by using a hydrophobic blocked isocyanate compound, moisture resistance such as adhesiveness can be further improved.
  • the blocking agent examples include pyrazole compounds such as 3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole and 4-nitro-3,5-dimethylpyrazole, and phenolic compounds such as phenol and cresol.
  • pyrazole compounds such as 3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole and 4-nitro-3,5-dimethylpyrazole
  • phenolic compounds such as phenol and cresol.
  • An aliphatic alcohol system such as methanol and ethanol, an active methylene system such as dimethyl malonate and acetylacetone, a mercaptan system such as butyl mercaptan and dodecyl mercaptan, an acid amide system such as acetanilide and acetate amide, ⁇ -caprolactam, ⁇ -valerolactam.
  • a blocking agent in which the reaction product with the isocyanate group becomes a hydrophilic group is not so preferable, and examples thereof include compounds such as sulfites, bicarbonates, and diethanolamine.
  • the upper limit of the dissociation temperature of the blocking agent is preferably 200 ° C, more preferably 180 ° C, still more preferably 160 ° C, particularly preferably 150 ° C, and most preferably 120 ° C.
  • the blocking agent is dissociated by heat addition in the drying step after the coating liquid is applied or in the case of the in-line coating method in the film forming step, and a regenerated isocyanate group is generated. As a result, the cross-linking reaction with other polyurethane resins and the like in the coating film proceeds, and the cross-linking state of the coating film is improved.
  • Examples of the blocking agent having a dissociation temperature of 120 ° C. or lower that the hydrophobic blocked isocyanate in the present invention can preferably contain include the above-mentioned pyrazole compounds such as 3,5-dimethylpyrazole and 3-methylpyrazole, and dimethyl malonate.
  • Examples thereof include malonic acid ester compounds such as diethyl malonate, acetone oxime, and methyl ethyl keto oxime. Of these, methyl ethyl ketooxime, malonic acid ester compounds, or pyrazole compounds are preferable from the viewpoint of moisture resistance and heat resistance and yellowing.
  • the hydrophobic blocked isocyanate is preferably bifunctional or higher, and trifunctional or higher functional blocked isocyanate is more preferable from the viewpoint of crosslinkability of the coating film.
  • the trifunctional or higher functional polyisocyanate which is a precursor of the hydrophobic blocked isocyanate in the present invention can be suitably obtained by introducing an isocyanate monomer.
  • an isocyanate monomer examples thereof include a bullet form, an isocyanurate form, and an adduct form obtained by modifying an isocyanate monomer such as an aromatic diisocyanate having two isocyanate groups, an aliphatic diisocyanate, an aromatic aliphatic diisocyanate, or an alicyclic diisocyanate.
  • the burette body is a self-condensate having a burette bond formed by self-condensation of an isocyanate monomer, and examples thereof include a burette body of hexamethylene diisocyanate.
  • the isocyanurate form is a trimer of an isocyanate monomer, and examples thereof include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, and a trimer of tolylene diisocyanate.
  • the adduct is a trifunctional or higher functional isocyanate compound obtained by reacting an isocyanate monomer with a trifunctional or higher low molecular weight active hydrogen-containing compound, for example, a compound obtained by reacting trimethylolpropane with hexamethylene diisocyanate.
  • Examples thereof include 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.
  • isocyanate monomer examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and 1,5.
  • Aromatic diisocyanates isophorone diisocyanates and 4,4-dicyclohexylmethane diisocyanates, alicyclic diisocyanates such as 1,3-bis (isocyanatemethyl) cyclohexane, hexamethylene diisocyanates, and 2,2,4-trimethylhexamethylene diisocyanates.
  • aliphatic diisocyanates such as. Aliphatic compounds, alicyclic isocyanates, and modified products thereof are preferable from the viewpoints of transparency, yellowing resistance, adhesiveness, and moisture heat resistance.
  • the blocked isocyanate compound itself in the present invention is hydrophobic and does not have water dispersibility. Therefore, it is necessary to use an emulsifier or the like separately from the blocked isocyanate compound to develop water dispersibility.
  • an emulsifier anionic, cationic, nonionic, amphoteric surfactants and the like can be used, but in this case, it is preferable to use anionic.
  • anionic surfactant By using an anionic surfactant, the dispersion stability of the blocked isocyanate compound can be improved.
  • a low molecular weight or high molecular weight type can be used as the anionic surfactant in the present invention.
  • Low-molecular-weight anionic surfactants include carboxylic acid type, sulfate ester type, sulfonic acid type, and phosphoric acid ester type.
  • carboxylic acid type include aliphatic monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acylsulfosin salts and N-acylglutamine salts
  • sulfate ester types include alkyl sulfates and polyoxys.
  • Examples of the sulfonic acid type include ethylene alkyl ether sulfate, oil and fat sulfate ester salt, and examples of the sulfonic acid type include dialkyl sulfosuccinate, alkane sulfonate, alpha olefin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, and N-acyl. Examples thereof include N-acyltaurine salts, and examples of the phosphate ester type include alkyl phosphates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkyl phenyl ether phosphates.
  • the polymer anionic surfactant includes polymers or copolymers such as acrylic acid, maleic acid and styrene sulfonic acid, which are unsaturated monomers having an anionic group, sulfonic acid groups, carboxylic acids, phosphinic acid and the like. Examples thereof include polyesters and polyurethane resins obtained by copolymerizing the monomers having the same.
  • a polyurethane resin having a carboxyl group it is preferable to use. More preferably, it has a core-shell structure in which a hydrophobic blocked isocyanate compound is used as a core and a polyurethane resin having a carboxyl group is used as a shell. These make it possible to maintain the long-term dispersion stability of the blocked isocyanate compound, and the dispersion stability is unlikely to decrease even when mixed with other resins or additives. Details of the core-shell structure will be described later.
  • the polyurethane resin in the present invention is preferably a water-dispersible polyurethane resin having at least a polyol component, a polyisocyanate component, and, if necessary, a carboxyl group consisting of a chain extender.
  • the carboxyl group of the polyurethane resin in the present invention is present in the molecule or in the side chain in order to impart water solubility or water dispersibility to the polyurethane resin.
  • the term "in the molecule” as used herein means a substance present in the main chain or at the end of the polyurethane resin.
  • the side chain is introduced onto the branched molecular chain after being synthesized and polymerized due to the presence of three or more terminal functional groups of any of the raw material components constituting the molecular chain. It is a thing. In the present invention, there is no problem even if a hydrophilic group other than the carboxyl group is introduced into the polyurethane resin.
  • a hydrophilic group other than the carboxyl group an anionic group typified by sulfonic acid, phosphonic acid, etc., a cationic group typified by a quaternary amine, and a nonionic group typified by an oxyalkylene group may be used. However, a nonionic group typified by an oxyalkylene group is preferable because it is easy to introduce and does not react with a carboxyl group.
  • the polyurethane resin having a carboxyl group in the present invention is mainly obtained by using a carboxyl group-containing polyol component as a component of the urethane resin.
  • a carboxyl group-containing polyol component include the following. Those having a relatively high molecular weight, for example, a carboxyl group-containing polyalkylene glycol, a carboxyl group-containing acrylic polyol, a carboxyl group-containing polyolefin polyol, a carboxyl group-containing polyester polyol, and the like can be used.
  • those having a relatively low molecular weight for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropane valeric acid and the like can be used. ..
  • dimethylolpropionic acid and dimethylolbutanoic acid are preferably used for introducing a carboxyl group.
  • the polyurethane resin having a carboxyl group preferably has an acid value of 10 to 60 mgKOH / g, and more preferably an acid value of 20 to 50 mgKOH / g.
  • the acid value is 10 mgKOH / g or more, the hydrophilicity of the polyurethane resin itself is improved, and water solubility or water dispersibility is maintained, which is preferable.
  • the acid value is 60 mgKOH / g or less, the water resistance of the coating layer is improved and there is no blocking problem due to moisture absorption, which is preferable.
  • hydrophilic groups other than the carboxyl group such as hydroxyl groups, oxyalkyl groups, sulfonic acids and phosphonic acids, are used.
  • a quaternary amine or the like may be introduced within a range in which the performance does not deteriorate.
  • the carboxyl group in the polyurethane resin may be neutralized with a basic compound.
  • the basic compound used for neutralization include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, and organic amine compounds.
  • an organic amine compound that easily dissociates from a carboxyl group by heating is preferable.
  • the organic amine compound include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, 2-ethylhexylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, trimethylamine and triethylamine.
  • Linear and branched 1,2 or tertiary amines with 1 to 20 carbon atoms such as triisopropylamine, tributylamine and ethylenediamine, cyclic amines such as morpholin, N-alkylmorpholin and pyridine, monoisopropanolamine and methylethanol.
  • cyclic amines such as morpholin, N-alkylmorpholin and pyridine
  • monoisopropanolamine and methylethanol examples thereof include hydroxyl group-containing amines such as amines, methylisopropanolamines, dimethylethanolamines, diisopropanolamines, diethanolamines, triethanolamines, diethylethanolamines and triethanolamines.
  • polyester polyol or a polycarbonate polyol in addition to the above-mentioned polyoxyalkylene glycol as the main polyol component used for synthesizing and polymerizing the urethane resin having a carboxyl group in the present invention.
  • the number average molecular weight of the polyester polyol or the polycarbonate polyol in the present invention is preferably 300 to 5000. It is more preferably 400 to 4000, and most preferably 500 to 3000. When it is 300 or more, the adhesiveness can be improved, which is preferable. When it is 5000 or less, fusion between the coating layers can be prevented (blocking resistance is improved), which is preferable.
  • the polyester polyol in the present invention is preferably an aliphatic or alicyclic group. Therefore, the dicarboxylic acid components of the polyester polyol include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Can be mentioned.
  • the diol component includes ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , 1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, neopentyl glycol and other aliphatic diols, cyclohexanedimethanol and other fats Examples include cyclic diols.
  • a long-chain fatty acid of adipic acid or higher and a long-chain diol of pentanediol or higher it is preferable to mainly use a long-chain fatty acid of adipic acid or higher and a long-chain diol of pentanediol or higher.
  • a trifunctional or higher functional polycarboxylic acid, polyol, unsaturated type, or aromatic component may be used as long as the physical properties are not deteriorated.
  • polycarbonate polyol in the present invention it is preferable to use an aliphatic polycarbonate polyol.
  • the aliphatic polycarbonate polyol include an aliphatic polycarbonate diol and an aliphatic polycarbonate triol, and an aliphatic polycarbonate diol can be preferably used.
  • the aliphatic polycarbonate diol used for synthesizing and polymerizing the urethane resin having a polycarbonate structure in the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5.
  • -Pentanediol 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol and other diols
  • examples thereof include aliphatic polycarbonate diols obtained by reacting one or more of them with carbonates such as dimethyl carbonate, ethylene carbonate and phosgene.
  • polyol components other than the above can also be used.
  • examples of other polyol components include polyether polyols, polyolefin polyols, dimer polyols, silicone polyols and the like.
  • Examples of the polyisocyanate used for the synthesis and polymerization of the water-dispersible urethane resin having a carboxyl group in the present invention include aromatic diisocyanates containing an aromatic ring such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate. , 1,3-Bis (isocyanatemethyl) cyclohexane and other alicyclic diisocyanates, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate and other aliphatic diisocyanates, or isocyanates produced from diisocyanates.
  • aromatic diisocyanates containing an aromatic ring such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate.
  • Examples thereof include modified polyisocyanates containing a nurate bond, a biurette bond or an allophanate bond, and polyisocyanates in which a single or a plurality of diisocyanates are previously added to trimethylol propane or the like.
  • modified polyisocyanates containing a nurate bond, a biurette bond or an allophanate bond and polyisocyanates in which a single or a plurality of diisocyanates are previously added to trimethylol propane or the like.
  • chain extender examples include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, and ethylenediamine. , Hexamethylenediamine, diamines such as piperazine, aminoalcohols such as monoethanolamine and diethanolamine, thioglycols such as thiodiethyleneglycol, and water. Further, if the amount is small, a polyol having three or more functional groups, a polyamine, or the like may be used.
  • glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol
  • polyhydric alcohols such as glycerin, trimethylolpropane, and
  • the solvent system is preferable from the viewpoint of using it as an emulsifier for the above-mentioned hydrophobic blocked isocyanate compound.
  • the solvent may remain in the aqueous dispersion or the solvent may be removed, it is preferable to remove the solvent from the viewpoint of the environment.
  • the method for producing a dispersion of a blocked isocyanate compound using a water-dispersible polyurethane resin having a carboxyl group as an emulsifier is not particularly limited, but water dispersion is carried out after mixing the hydrophobic blocked isocyanate compound and the polyurethane resin having a carboxyl group. It is preferable to do so from the viewpoint of dispersion stability of the blocked isocyanate compound.
  • a blocked isocyanate compound is used as a core and polyurethane resin, such that it is mixed with a blocked isocyanate compound, water-dispersed, and then polyamine or the like is added to form a chain extender in a water-dispersed state to form a polyurethane resin.
  • An aqueous dispersion having a core-shell structure having a shell is preferable.
  • the water-dispersible polyurethane resin having a carboxyl group in the present invention may have a reactive group such as blocked isocyanate at the terminal or side chain in order to improve the hardness.
  • polyester resin used in combination with the coating layer in the present invention is not particularly limited, but a polyester resin containing 50 mol% or more of the aromatic dicarboxylic acid in the acid component is preferable from the viewpoint of hydrolysis resistance and physical characteristics.
  • aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid and the like.
  • Other acid components include aliphatic dicarboxylic acids such as adipic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, acid anhydrides such as maleic anhydride, or trimellitic acid and trimesin, as required.
  • a tricarboxylic acid such as an acid can be used.
  • the diol component it is preferable that ethylene glycol is contained in an amount of 30 mol% or more in the diol component.
  • Other diol components include linear aliphatic diols such as 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, or 1,2-propanezyl and 1,3-butane.
  • Diol branched aliphatic diols such as 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, alicyclic diols such as cyclohexanedimethanol, diethylene glycol, dipropylene glycol and the like.
  • alicyclic diols such as cyclohexanedimethanol, diethylene glycol, dipropylene glycol and the like.
  • examples thereof include polyoxyalkylene glycols such as diglycol and polyethylene glycol, and polyoxyalkylene glycol derivatives such as bisphenol A.
  • a hydrophilic group is present on the molecular skeleton in order to impart water dispersibility to the polyester resin.
  • a dicarboxylic acid in which a phosphonic acid group, a sulfonic acid group or the like is introduced into a dicarboxylic acid component may be used, or a polyether such as polyethylene glycol may be used as a diol component.
  • the carboxyl group may be introduced into the polyester skeleton by reacting the hydroxyl group terminal of the polymerized polyester with the polycarboxylic acid anhydride.
  • the sulfonic acid group-containing dicarboxylic acid in the dicarboxylic acid component in the range of 1 to 10 mol%, and examples of the sulfonic acid group-containing dicarboxylic acid include sulfoterephthalic acid, 5-sulfoisophthalic acid, and 5-sodium sulfoisophthalic acid. Acids and the like can be mentioned.
  • the present invention may be used in combination with other resins as long as the performance is not affected.
  • the resin to be used in combination include a non-carboxyl group-containing polyurethane resin, an alkyd resin, an acrylic resin, a cellulose resin, a polyolefin resin, and a polyacetal resin.
  • a cross-linking agent other than the hydrophobic blocked isocyanate compound in the present invention may be used in combination.
  • cross-linking agents hydrophilic blocked isocyanate-based, epoxy-based, melamine-based, oxazoline-based, carbodiimide-based and the like can be used.
  • another cross-linking agent in the range of 20% by mass or less, the cross-linking state can be adjusted to reduce the influence on the adhesiveness and the like, and the durability such as moisture and heat resistance can be further improved.
  • the hydrophobic blocked isocyanate compound can adjust the cross-linking state by changing the cross-linking reaction start temperature depending on the composition of the blocking agent. It is preferable to select different blocking agents.
  • additives such as surfactants, antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, organic lubricants, and pigments are used as long as the effects of the present invention are not impaired.
  • Dyes, organic or inorganic particles, antistatic agents, nucleating agents and the like may be added.
  • the particles contained in the coating layer include, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof, and other general ones.
  • Inorganic particles such as calcium phosphate, mica, hectrite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride and others, and organic particles such as styrene, acrylic, melamine, benzoguanamine and silicone. Examples include polymer particles.
  • the average particle size of the other particles in the coating layer is preferably 0.02 to 2.00 ⁇ m, more preferably 0.04 to 1. It is 0.00 ⁇ m.
  • the average particle size of the inert particles is 0.04 ⁇ m or more, it becomes easy to form irregularities on the film surface, so that the handleability such as slipperiness and winding property of the film is further improved, and the film is bonded. The workability of the above is good and is preferable.
  • the average particle size of the inert particles is 2.00 ⁇ m or less, the particles are less likely to fall off, which is preferable.
  • the particle concentration in the coating layer is preferably 1 to 20% by mass in the solid component.
  • the average particle size of the other particles was measured by observing the particles in the cross section of the laminated polyester film with a scanning electron microscope, observing 30 particles, and using the average value as the average particle size.
  • the shape of the other particles is not particularly limited as long as it satisfies the object of the present invention, and spherical particles and amorphous non-spherical particles can be used.
  • the particle size of the amorphous particles can be calculated as the equivalent circle diameter.
  • the equivalent circle diameter is a value obtained by dividing the observed particle area by ⁇ , calculating the square root, and doubling it.
  • PET film base material a polyethylene terephthalate (hereinafter, may be abbreviated as PET) film base material. Not limited to.
  • the PET resin After the PET resin is sufficiently vacuum-dried, it is supplied to an extruder, and the molten PET resin at about 280 ° C. is melt-extruded into a sheet on a rotary cooling roll, cooled and solidified by an electrostatic application method, and unstretched PET. Get a sheet.
  • the unstretched PET sheet may have a single-layer structure or a multi-layer structure by a coextrusion method.
  • the obtained unstretched PET sheet is uniaxially stretched or biaxially stretched to orient the crystals.
  • a roll heated to 80 to 120 ° C. is stretched 3.0 to 5.0 times in the longitudinal direction to obtain a uniaxially stretched PET film, and then the end of the film is gripped with a clip. Then, it is guided to a hot air zone heated to 80 to 180 ° C. and stretched 3.0 to 5.0 times in the width direction.
  • the unstretched PET sheet is stretched 3.0 to 5.0 times in the tenter. After stretching, the crystals are continuously led to a heat treatment zone at 180 to 230 ° C. and heat-treated to complete the crystal orientation.
  • any known method can be used as the method for applying the coating liquid to the PET film.
  • reverse roll coat method gravure coat method, kiss coat method, die coater method, roll brush method, spray coat method, air knife coat method, wire bar coat method, pipe doctor method, impregnation coat method, curtain coat method, etc. Be done. These methods can be applied alone or in combination.
  • the thickness of the coating layer can be appropriately set in the range of 0.001 to 2.00 ⁇ m, but the range of 0.01 to 1.00 ⁇ m is preferable in order to achieve both workability and adhesiveness. It is more preferably 0.02 to 0.80 ⁇ m, and even more preferably 0.05 to 0.50 ⁇ m.
  • the thickness of the coating layer is 0.001 ⁇ m or more, the adhesiveness is good and it is preferable.
  • 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 2.0%, more preferably 1.8%, still more preferably 1.5%, and particularly preferably 1.2%.
  • the haze is 2.0% or less, it is preferable in terms of transparency, and it can be suitably used for optical film applications where transparency is required.
  • the haze is preferably small, but may be 0.1% or more, or 0.3% or more.
  • a closed curve that does not intersect with themselves, and those surrounded by a maximum width of 200 ⁇ m or more a.
  • the inside of a closed curve is a recess c.
  • the maximum depth of the outer peripheral part and the inner part of the closed curve is 70% or more of the coating layer thickness.
  • Workman The depth variation of the internal region of the closed curve is in the range of less than 50% of the coating layer thickness.
  • 50% or more of the closed curve has a gradient of 60 ° or more from the horizontal plane inside the curve. The number of peeling defects determined above was converted per 1 m 2.
  • coating film thickness it is possible to use a value calculated from the total solid content concentration of the coating liquid, a resin content specific gravity, a coating amount, a draw ratio, etc., or an analysis value from an SEM photograph of a film cross section.
  • Adhesion with UV ink A UV ink [manufactured by T & K TOKA Co., Ltd., trade name "BEST CURE UV161 indigo S” or “BEST CURE UV161 white S”] is used on the coating layer of the laminated polyester film. Printing was performed with an ink pipette 4 scales and a 2-split roll using a printing machine [manufactured by Ming Seisakusho Co., Ltd., trade name "RI tester”], and then 100 mJ / cm 2 using a high-pressure mercury lamp on the film coated with the ink layer. The UV curable ink was cured by irradiating with the ultraviolet rays of.
  • a cellophane adhesive tape (manufactured by Nichiban, No. 405; 24 mm width) is attached to the cut surface in the shape of a grid. After that, the cellophane adhesive tape is vertically peeled off from the ink layer surface of the ink laminated film, the number of squares peeled off from the ink layer surface of the ink laminated film is visually counted, and the ink layer and the film substrate adhere to each other from the following formula. Seeking sex.
  • Ink adhesion (%) 100- (number of peeled squares) Ink adhesion (%) was classified as follows, and ⁇ and ⁇ were regarded as acceptable. ⁇ : 100%, ⁇ : 99-96%, ⁇ : 95-80%, ⁇ : 79-0%
  • Adhesion to the hard coat layer Opstar Z7503 (manufactured by Arakawa Chemical Industry Co., Ltd.), which is a UV curable hard coat agent, is applied onto the coated layer of the laminated polyester film using a # 5 wire bar, and 80 It was dried at ° C for 1 minute.
  • the applied film was irradiated with ultraviolet rays of 100 mj / cm 2 using a high-pressure mercury lamp to obtain a hard-coated film.
  • using a cutter guide with a gap spacing of 2 mm 100 grid-like cuts that penetrate the hardcourt layer and reach the film substrate are made on the hardcourt layer surface.
  • a cellophane adhesive tape (manufactured by Nichiban, No.
  • the cellophane adhesive tape is vertically peeled off 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 is visually counted, and the hard coat layer and the film are counted from the following formula.
  • those that were partially peeled out among the squares were also counted as the peeled squares, and the hard coat adhesion was obtained as shown in the following formula.
  • the hard coat adhesion was 100 (%).
  • Hardcourt adhesion (%) 100- (number of peeled squares) Hardcourt adhesion (%) was classified as follows, and ⁇ and ⁇ were judged as acceptable. ⁇ : 100%, ⁇ : 99-96%, ⁇ : 95-80%, ⁇ : 79-0%
  • a UV ink-coated or hard-coated film prepared in the same manner as in (5) and (6) above is placed in an environment of 80 ° C. and 80% RH so that the coated surface is vertical and another film is applied to the coated surface. It was left for 500 hours without any contact. After the treatment, it was left in an environment of 23 ° C. and 65% RH for 10 minutes without contact with other films or the like on the coated surface. Immediately after the lapse of time, the adhesion of the coated surface was evaluated in the same manner as described above.
  • reaction was further stirred at 80 ° C. for 2 hours. After that, the infrared spectrum of the reaction solution was measured, and it was confirmed that the absorption of the isocyanate group disappeared. As a result, a methyl ethyl ketone solution of the blocked isocyanate compound BI-5 having a nonionic group was obtained.
  • This polyurethane resin CS-1 is a polyurethane in which the core is a blocked isocyanate compound BI-1 and the shell is formed from an anionic prepolymer P-1.
  • This polyurethane resin CS-2 is a polyurethane in which the core is a blocked isocyanate compound BI-2 and the shell is formed from an anionic prepolymer P-2.
  • This polyurethane resin CS-3 is a polyurethane in which the core is a blocked isocyanate compound BI-3 and the shell is formed from an anionic prepolymer P-3.
  • aqueous dispersion (CS-4WD) of a core-shell type aqueous polyurethane resin CS-4 having a solid content concentration of 30% by mass was prepared. Obtained.
  • This polyurethane resin CS-4 is a polyurethane in which the core is a blocked isocyanate compound BI-4 and the shell is formed from an anionic prepolymer P-1.
  • This polyurethane resin CS-5 is a polyurethane having a core of a blocked isocyanate compound BI-1 and a shell made of a nonionic prepolymer P-4.
  • an aqueous dispersion (CS-6WD) of a core-shell type aqueous polyurethane resin CS-6 having a solid content concentration of 30% by mass was prepared. Obtained.
  • the polyurethane resin CS-6 is a polyurethane having a nonionic blocked isocyanate compound BI-5 as a core and an anionic prepolymer P-1 as a shell.
  • Polyurethane resin [Manufacturing of polyurethane resin PU-1] 437.2 parts by mass of polycarbonate diol with a number average molecular weight of 2000, 192.2 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, 60.8 parts by mass of dimethylolpropionic acid in a flask equipped with a stirrer, a thermometer, and a reflux cooling tube. , 13.0 parts by mass of 1,6-hexanediol and 250 parts by mass of methyl ethyl ketone as a solvent were charged, stirred at 80 ° C.
  • polyester resin PE-1 (Manufacturing of polyester resin PE-1] 95 parts by mass of dimethyl terephthalate, 95 parts by mass of dimethyl isophthalate, 35 parts by mass of ethylene glycol, 145 parts by mass of neopentyl glycol, 0.1 part by mass of zinc acetate and 0.1 part by mass of antimony trioxide were charged into a reaction vessel and 180 ° C. The transesterification reaction was carried out over 3 hours. Next, 6.0 parts by mass of 5-sodium sulfoisophthalic acid was added, and the esterification reaction was carried out at 240 ° C. for 1 hour, and then under reduced pressure at 250 ° C. (1.33 to 0.027 kPa) for 2 hours.
  • the polycondensation reaction was carried out to obtain a polyester resin (PE-1) having a molecular weight of 19,500. 300 parts by mass of this polyester resin (PE-1) and 140 parts by mass of butyl cellosolve were stirred at 160 ° C. for 3 hours to obtain a viscous melt, and water was gradually added to the melt to give a uniform pale white color after 1 hour.
  • a polyester resin aqueous dispersion (PE-1WD) having a solid content of 15% by mass was prepared.
  • polyester resin PE-2 [Manufacturing of polyester resin PE-2] Add 105 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, 50 parts by mass of ethylene glycol, 36 parts by mass of hexanediol, 0.1 part by mass of zinc acetate and 0.1 part by mass of antimony trioxide into the reaction vessel, and 3 at 180 ° C. The transesterification reaction was carried out over time. Next, 8.6 parts by mass of 5-sodium sulfoisophthalic acid and 8 parts by mass of sebacic acid were added, and an esterification reaction was carried out at 240 ° C. for 1 hour, and then 1.33 to 0.
  • a polycondensation reaction was carried out at 027 kPa) for 2 hours to obtain a polyester resin (PE-2) having a molecular weight of 18,000. 300 parts by mass of this polyester resin (PE-2) and 140 parts by mass of butyl cellosolve were stirred at 160 ° C. for 3 hours to obtain a viscous melt, and water was gradually added to the melt to give a uniform pale white color after 1 hour.
  • a polyester resin aqueous dispersion (PE-2WD) having a solid content of 15% by mass was prepared.
  • a monomer mixture consisting of parts by mass and a polymerization initiator solution consisting of 18.0 parts by mass of 2,2'-azobis (2-amidinopropane) dihydrochloride and 170.0 parts by mass of water as a polymerization initiator are added dropwise.
  • the solution was dropped from the funnel under a nitrogen atmosphere over 2 hours while keeping the inside of the flask at 80 ° C. After completion of the dropping, the mixture was stirred at 80 ° C. for 5 hours and then cooled to room temperature.
  • An appropriate amount of water was added to prepare an oxazoline-based cross-linking agent aqueous dispersion (OX-1WD) having a solid content of 40% by mass.
  • OX-1WD oxazoline-based cross-linking agent aqueous dispersion
  • (acrylic resin) T-butylperoxy-2-ethylhexano as a polymerization initiator in 356 parts by mass of methyl methacrylate, 16 parts by mass of acrylic acid, 5 parts by mass of normal butyl acrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and 372 parts by mass of methyl ethyl ketone. While stirring by adding 2 parts by mass of ate, the temperature was raised to 50 ° C. and held for 120 minutes, and then the temperature was raised to 70 ° C. and held for 180 minutes.
  • particle PA-1 colloidal silica (Snowtex ZL; manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 80 nm and a solid content concentration of 40% by mass was used as it was as the particles (PA-1) solution.
  • Particle PA-2 As the particles (PA-2), colloidal silica (Snowtex XL; manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 40 to 60 nm having a solid content concentration of 40% by mass was used as it was as the particles (PA-2) solution.
  • colloidal silica Snowtex XL; manufactured by Nissan Chemical Industries, Ltd.
  • the above antimony trioxide solution was used as a polycondensation catalyst in this BHET mixture, and the amount of antimony atoms was added to 0.04 mol% with respect to the acid component in the polyester, and then 250 under normal pressure under a nitrogen atmosphere. The mixture was stirred at ° C for 10 minutes. After that, the pressure of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) while raising the temperature to 280 ° C. over 60 minutes, and the polycondensation reaction was further carried out at 280 ° C. and 13.3 Pa for 68 minutes to carry out the intrinsic polycondensation reaction.
  • polyester resin E-2 for base material
  • antimony trioxide solution As a polycondensation catalyst, a mixture of the above-mentioned aluminum compound solution and phosphorus compound solution was used, and 0.014 mol% and phosphorus atoms were used as aluminum atoms and phosphorus atoms, respectively, with respect to the acid component in the polyester. It was polymerized in the same manner as the polyester resin E-1 except that it was added so as to be 0.028 mol%. However, by setting the polymerization time to 68 minutes, a polyester resin E-2 having an intrinsic viscosity (IV) of 0.61 dl / g and substantially containing no particles was obtained.
  • IV intrinsic viscosity
  • Example 1 (1) Preparation of coating liquid
  • the following coating agent was mixed with a mixed solvent (80/20 parts by mass) of water and isopropanol to adjust the total amount to 100 parts by mass.
  • the solid content mass ratio of the aqueous dispersion of the blocked isocyanate compound BI-1 (BI-1WD-A) / the aqueous dispersion of the polyurethane resin (PU-1WD) / the aqueous dispersion of the polyester resin (PE-1WD) is 25/45. / 30,
  • the total solid resin content concentration was 4% by mass.
  • the solid content mass ratios of the particles PA-1 and the particles PA-2 were set to 0.5 and 8, respectively, with respect to the solid content 100 of the above-mentioned resin or the like.
  • a 10% aqueous solution of a silicone-based surfactant was added to the coating liquid in an amount of 1% by mass.
  • Table 1 shows the compounding ratios of the resins and the like in the coating liquids of Examples and Comparative Examples.
  • Mixed solvent water / isopropanol
  • 20 parts by mass water dispersion of polyester resin (PE-1WD) 8.00 parts by mass particles
  • PA-1 solution 0.05 parts by mass particles
  • PA- 2 solutions 0.80 parts by mass
  • This unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a peripheral speed difference to obtain a uniaxially stretched PET film.
  • the coating liquid was applied to one side of the PET film so that the coating amount was 6.0 g / m 2, and heat-treated at 90 ° C. for 3 seconds and 40 ° C. for 3 seconds to dry. Further, the surface of the coating layer of the film was brought into contact with a tension control roll (surface roughness: 0.4S) having a diameter of 200 mm and having been hard chrome plated.
  • the running conditions at this time were a running speed of 20 m / min, a winding angle of 60 degrees, and a running tension of 400 to 500 N / m.
  • the film was stretched 4.0 times in the width direction at 110 ° C., and heated at 230 ° C. for 5 seconds with the width direction of the film fixed. Further, a relaxation treatment in the width direction of 3% was performed to obtain a 100 ⁇ m laminated polyester film.
  • Table 2 The evaluation results of this film are shown in Table 2.
  • Examples 2 to 9 A laminated polyester film was obtained in the same manner as in Example 1 except that the coating liquid of Example 1 was changed according to the types of resins and additives of each Example of Table 1 and the mixing amount ratio of each.
  • Example 10 A laminated polyester film was obtained in the same manner as in Example 1 except that E-2 was used instead of the polyester resin E-1 as the film raw material polymer.
  • Example 1 A laminated polyester film was obtained in the same manner as in Example 1 except that the coating liquid of Example 1 was changed according to the types of resins and additives of each Comparative Example in Table 1 and the mixing amount ratios.
  • Table 2 summarizes the evaluation results of each example and comparative example.

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Abstract

 La présente invention aborde le problème de la fourniture d'un film de polyester multicouche qui a une couche de revêtement qui a une excellente transparence (faible trouble) et une excellente durabilité, tout en étant supprimée dans des défauts de film de revêtement, et qui présente une adhésivité élevée qui est la plus adaptée dans différents domaines tels que des matériaux optiques, des emballages et des étiquettes. La présente invention concerne un film de polyester multicouche qui comporte un film de revêtement qui est formé à partir d'un liquide de revêtement contenant une dispersion aqueuse d'un composé isocyanate bloqué hydrophobe qui est hydrophilisé au moyen d'un agent émulsifiant anionique, une résine de polyuréthane hydrodispersible comportant un groupe carboxyle, et une résine de polyester hydrodispersible, les défauts de séparation du film de revêtement étant inférieurs à 5,0 défauts/m2.
PCT/JP2021/020518 2020-06-19 2021-05-28 Film de polyester multicouche WO2021256224A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
WO2009113412A1 (fr) * 2008-03-14 2009-09-17 日本ポリウレタン工業株式会社 Composition d'émulsion contenant un isocyanate bloqué, procédé pour produire celle-ci, couche primaire à base aqueuse pour substrat poreux, et composition de revêtement au four à base aqueuse
JP2011156848A (ja) * 2010-02-04 2011-08-18 Toyobo Co Ltd 積層ポリエステルフィルム
JP2015205440A (ja) * 2014-04-19 2015-11-19 三菱樹脂株式会社 積層ポリエステルフィルム
JP2019503075A (ja) * 2015-12-23 2019-01-31 アグフア−ゲヴエルト 太陽電池モジュール用のバックシート
JP2019137757A (ja) * 2018-02-08 2019-08-22 旭化成株式会社 ブロックイソシアネート組成物、水分散体、水系コーティング組成物、コーティング基材及び凝集方法

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JPS60199648A (ja) 1984-03-23 1985-10-09 帝人株式会社 易接着性ポリエステルフイルム
JP2005154674A (ja) 2003-11-28 2005-06-16 Nippon Polyurethane Ind Co Ltd 水性一液コーティング剤用ポリウレタンエマルジョンの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009113412A1 (fr) * 2008-03-14 2009-09-17 日本ポリウレタン工業株式会社 Composition d'émulsion contenant un isocyanate bloqué, procédé pour produire celle-ci, couche primaire à base aqueuse pour substrat poreux, et composition de revêtement au four à base aqueuse
JP2011156848A (ja) * 2010-02-04 2011-08-18 Toyobo Co Ltd 積層ポリエステルフィルム
JP2015205440A (ja) * 2014-04-19 2015-11-19 三菱樹脂株式会社 積層ポリエステルフィルム
JP2019503075A (ja) * 2015-12-23 2019-01-31 アグフア−ゲヴエルト 太陽電池モジュール用のバックシート
JP2019137757A (ja) * 2018-02-08 2019-08-22 旭化成株式会社 ブロックイソシアネート組成物、水分散体、水系コーティング組成物、コーティング基材及び凝集方法

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