WO2022176744A1 - 空洞含有ポリエステル系フィルム - Google Patents

空洞含有ポリエステル系フィルム Download PDF

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Publication number
WO2022176744A1
WO2022176744A1 PCT/JP2022/005189 JP2022005189W WO2022176744A1 WO 2022176744 A1 WO2022176744 A1 WO 2022176744A1 JP 2022005189 W JP2022005189 W JP 2022005189W WO 2022176744 A1 WO2022176744 A1 WO 2022176744A1
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Prior art keywords
layer
void
polyester film
resin
film
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PCT/JP2022/005189
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English (en)
French (fr)
Japanese (ja)
Inventor
芽衣 松村
栄二 熊谷
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東洋紡株式会社
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Priority to CN202280015413.XA priority Critical patent/CN116887985A/zh
Priority to JP2023500780A priority patent/JPWO2022176744A1/ja
Publication of WO2022176744A1 publication Critical patent/WO2022176744A1/ja

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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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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

Definitions

  • the present invention contains cavities of an optimal size, is not only lightweight, but also has excellent hiding properties, whiteness, film forming properties, and thermal dimensional stability, and has ink adhesion and antistatic properties as information recording materials and printing materials.
  • the present invention relates to an easy-adhesive, void-containing polyester film having excellent properties.
  • Synthetic paper which is a paper substitute whose main component is synthetic resin, is superior to natural paper in terms of water resistance, moisture absorption dimensional stability, and surface stability, and is used for labels, stickers, posters, recording paper, and packaging materials. etc., are used in many ways.
  • Polyethylene resins, polypropylene resins, and polyester resins are used as the main raw materials for synthetic paper.
  • polyester resins represented by polyethylene terephthalate, have excellent mechanical and thermal properties. As such, it has been used in a wide range of applications.
  • Methods of obtaining a film with functions similar to paper generally include a method of containing a large amount of fine cavities inside the film, and surface treatments such as sandblasting, chemical etching, and matting on a flat film.
  • a method of roughening the surface by performing Among these methods the former method, which contains a large amount of fine cavities inside the film, not only provides paper-like hiding power and whiteness, but also reduces the weight of the film itself, thereby reducing the cost per unit area. It is widely used due to its merits, such as the fact that it can be suppressed, and that it provides appropriate flexibility and cushioning properties, resulting in excellent image clarity during printing.
  • an incompatible thermoplastic resin (hereinafter referred to as an incompatible resin) is mixed in the polyester resin, so that the polyester resin A melt having a sea-island structure in which an incompatible resin is dispersed is obtained. Then, an unstretched sheet is formed by extrusion from a die and stretched in at least one axial direction to develop voids due to interfacial peeling between the polyester-based resin and the incompatible resin.
  • Polyolefin-based resins such as polyethylene-based resins, polypropylene-based resins, and polymethylpentene-based resins (see, for example, Patent Documents 1 to 3) are examples of island component incompatible resins for polyester-based resins that are sea components. ) and polystyrene resins (see, for example, Patent Documents 4 and 5) are preferably used.
  • polypropylene resins are particularly preferable from the viewpoint of cavity development and cost performance.
  • the polyester film has high insulation properties, so the static electricity during various processes may cause ink to come off due to the adsorption of dust, and frictional electrification may cause the film to peel off. Problems such as poor feeding due to adsorption often lead to troubles during printing and the like.
  • the object of the present invention is to improve the above-mentioned problems in the conventional technology, contain cavities of an optimal size, and not only have light weight, but also have excellent hiding properties, whiteness, film-forming properties, and thermal dimensional stability.
  • the present inventors have found that by controlling the specific gravity, elastic modulus, and thickness from the amount of polypropylene resin added and the conditions during stretching, wrinkles can be reduced by controlling self-weight deflection and bending resistance. It was found that it is possible to suppress the occurrence of distortion. As a result, the present inventors have found that a void-containing polyester film can be obtained that does not cause wrinkles or distortion when the label is fed out or wrapped while maintaining the concealability and whiteness of the void-containing polyester film. In addition, the present inventors have found that a functional layer having excellent ink adhesion and antistatic properties can be used to obtain a film that does not cause troubles during the processing steps in applications such as labels.
  • the void-containing polyester film of the present invention has the following constitution.
  • the void-containing polyester film according to any one of claims 1 to 5 having an apparent density within the range of 0.8 to 1.2.
  • ADVANTAGE OF THE INVENTION it is possible to provide highly rigid synthetic paper that is less likely to cause wrinkles and distortion, etc. that can be used for applications such as labels that are excellent in concealability, whiteness, and printability, and that has excellent ink adhesion. It has easy adhesion suitable for information recording materials and printing materials, and antistatic properties that make it difficult for troubles to occur during processing.
  • the polyester resin that is the main component of the layers A and B is a polymer synthesized from a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative.
  • polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, and polyethylene terephthalate is preferred from the viewpoints of mechanical properties, heat resistance, cost, and the like.
  • polyester resins may be copolymerized with other components as long as the object of the present invention is not impaired.
  • copolymerizable components include dicarboxylic acid components such as isophthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid, and ester-forming derivatives thereof.
  • Diol components include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol.
  • polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol. The amount of copolymerization is preferably within 10 mol %, more preferably within 5 mol %, per constituent repeating unit.
  • the polyester-based resin of the present invention As a method for producing the polyester-based resin of the present invention, first, using the aforementioned dicarboxylic acid or its ester-forming derivative and the diol or its ester-forming derivative as main starting materials, an esterification or transesterification reaction is carried out according to a conventional method. After carrying out, the method of manufacturing by further performing a polycondensation reaction under high temperature and pressure reduction, etc. are mentioned.
  • the intrinsic viscosity of the polyester-based resin pellets of the present invention is preferably in the range of 0.50 to 0.9 dl/g, more preferably 0.55 to 0.85 dl/g from the viewpoint of film-forming properties and recyclability. is in the range.
  • thermoplastic resin which is incompatible with the polyester-based resin used in the present invention is mixed uniformly in the polyester-based resin in a dispersed state and causes separation at the interface with the base resin during stretching, which is a source of cavity formation.
  • a polypropylene resin is used.
  • the preferred amount of the immiscible resin to be blended varies depending on the amount of voids required for the film to be finally obtained and the stretching conditions. Less than 40% by mass, more preferably selected from the range of 5 to 30% by mass. When it is 3% by mass or more, a sufficient amount of voids generated in the stretching process can be ensured, and satisfactory lightness, flexibility, drawability, writability, etc. can be obtained. On the other hand, if it is less than 40% by mass, it is possible to avoid a significant decrease in stretchability, and to exhibit excellent heat resistance, strength, and stiffness (elastic force).
  • these polyester resins or polypropylene resins may contain small amounts of other polymers, antioxidants, heat stabilizers, matting agents, pigments, ultraviolet absorbers, Fluorescent whitening agents, plasticizers, other additives, and the like may be contained.
  • an antioxidant or a heat stabilizer in order to suppress oxidative deterioration of the polypropylene resin.
  • the types of antioxidants and heat stabilizers are not particularly limited, but include, for example, hindered phenols, phosphorus, hindered amines, etc. These may be used alone or in combination.
  • the amount to be added is preferably in the range of 1 to 50000 ppm.
  • the void-containing polyester-based film contains inorganic particles in the polyester-based resin or the immiscible resin as necessary in order to improve hiding power and whiteness.
  • the inorganic particles include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, titanium oxide, and zinc sulfide. Barium is preferred.
  • these inorganic particles may be used singly or in combination of two or more. These particles can be included in the film by adding them in advance to the polyester-based resin or to the incompatible resin.
  • the method of mixing the inorganic particles with the polyester resin or the immiscible resin is not particularly limited. and a method of dry-blending a polyester resin and an incompatible resin, followed by melt-kneading using various general kneaders to form a masterbatch.
  • the void-containing polyester film of the present invention is composed of a composition containing a polyester resin and an incompatible resin as a layer structure, and contains inorganic particles on both sides of the layer (A layer) containing voids inside. It has a laminated structure in which a layer (B layer) made of polyester resin is laminated.
  • a layer (B layer) made of polyester resin is laminated.
  • the layer A containing the immiscible resin is exposed on the surface, some of the exposed immiscible resin particles may cause process contamination such as roll contamination.
  • the A layer contains the recovered raw material, by covering it with the B layer containing the inorganic pigment, it has the effect of preventing the deterioration of the whiteness.
  • the ratio of the sum of the thicknesses of the B layers laminated on both sides of the A layer is preferably in the range of 1 to 40% of the thickness of the entire film from the viewpoint of suppressing the appearance of voids and the exposure of incompatible resins. , 5 to 30%.
  • the sum of the thicknesses of the B layers is 1% or more, exposure of the incompatible resin can be suppressed, which is preferable.
  • the sum of the thicknesses of the B layers is 40% or less, cavities can be formed to obtain sufficient lightness and cushioning properties.
  • the inorganic particles contained in the layer B include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, titanium oxide, zinc sulfide and the like. , titanium oxide, calcium carbonate and barium sulfate are preferred, and titanium oxide is particularly preferred. In addition, these inorganic particles may be used singly or in combination of two or more. These particles can be included in the film by adding them to the polyester resin in advance.
  • the upper limit of the average particle size of the inorganic particles contained in the B layer is preferably 5.0 ⁇ m, more preferably 3.0 ⁇ m, particularly from the viewpoint of printing quality when providing a printed layer or the like in post-processing. Preferably it is 2.5 ⁇ m.
  • the lower limit of the average particle size of the inorganic particles is preferably 0.1 ⁇ m, particularly preferably 0.2 ⁇ m, from the viewpoint of slipperiness and concealability in the film production process and post-processing process.
  • the amount of the inorganic particles added in the layer B is preferably 5% by mass or more and 40% by mass or less, more preferably in the range of 7 to 30% by mass.
  • the content of the inorganic particles in the layer B is preferably 1% by mass or more and 30% by mass or less, more preferably in the range of 2 to 20% by mass.
  • the layer A a self-regenerating raw material composed of selvages generated in the film-forming process and waste films generated due to breakage troubles.
  • the amount of the self-regenerating raw material to be added is preferably 5 to 60% by weight based on the total amount of each composition in the A layer from the viewpoints of raw material cost reduction, whiteness and film formability.
  • the B layer may contain a self-regenerating raw material, but from the viewpoint of deterioration of whiteness and exposure of the incompatible resin in the self-regenerating raw material, it is preferable not to contain it.
  • the easy-adhesive polyester film of the present invention has, on at least one surface thereof, an ion-conducting antistatic agent, a polycarbonate urethane resin, and a polyester resin, in order to improve the migration of the antistatic agent to the back surface and the adhesion to UV ink.
  • An easy-adhesion layer formed by curing a composition containing is laminated.
  • the easy adhesion layer is thought to be formed by curing a cationic antistatic agent or anionic antistatic agent, a polycarbonate urethane resin, or a polyester resin, but the chemical structure itself after curing cannot be expressed. Since it is difficult, it is expressed as being formed by curing a composition containing a cationic or anionic antistatic agent, a polycarbonate urethane resin, and a polyester resin.
  • the easy-adhesion layer may be provided on both sides of the polyester film substrate, or may be provided on only one side of the polyester film substrate and a different resin coating layer may be provided on the other side.
  • the easy-adhesion layer surface of the easy-adhesion polyester film has antistatic properties such that the surface resistivity is 1.0 ⁇ 10 13 ⁇ /sq or less.
  • the surface resistivity of the easy-adhesion layer surface is 1.0 ⁇ 10 13 ⁇ /sq or less, there is no adsorption of dust due to friction or static electricity generated during peeling, resulting in good print quality and high print quality. It is preferable because there is no scattering of toner particles.
  • the films are charged and attracted to each other, it is possible to prevent phenomena such as poor clearing and double feeding during transportation, which is preferable.
  • the surface resistivity of the easy-adhesion layer surface is more preferably 5.0 ⁇ 10 12 ⁇ /sq or less, still more preferably 1.0 ⁇ 10 12 ⁇ /sq or less.
  • the surface specific resistance value is 1.0 ⁇ 10 8 ⁇ /sq or more, the polarity does not become too high and the easy adhesion with various inks is good, which is preferable. It is more preferably 5.0 ⁇ 10 8 ⁇ /sq or more, and particularly preferably 1.0 ⁇ 10 9 ⁇ /sq or more.
  • an antistatic agent capable of suppressing migration to the back surface of other articles or the film itself with which it comes into contact is preferred.
  • the functional group is nonionic such as sorbitan type, ether type, ester type, sorbitol type, glucose type, etc.; , anionic surfactants such as alkyl sulfate type, alkyl phosphate type, phosphate ester salt type and sulfate ester salt type, and amphoteric surfactant types such as betaine type, amino acid type and amino sulfate type, or polymer types. .
  • the counter ion of the quaternary ammonium base is not particularly limited as long as it is an anionic compound, but is preferably halogen ion, mono- or polyhalogenated alkyl ion, nitrate ion, sulfate ion. , an alkylsulfate ion, a sulfonate ion or an alkylsulfonate ion, preferably the stability of the surface specific resistance value, the stability of the coating liquid, the ink adhesion, and the migration of the antistatic agent to other articles or the back surface Ethosulfate salts are preferred for suppressing
  • polymers may be homopolymers or copolymers.
  • Known copolymerizable monomers can be used to produce these polymers.
  • an antistatic agent having a linear alkyl group is preferable. It is preferably an antistatic agent having a class ammonium base.
  • the number of carbon atoms in the alkyl chain is preferably 10 to 25, more preferably 12 to 19, 14 to 18 are particularly preferred. In view of the interaction between the same molecules and the suppression of migration to the back due to the molecular length, the above range is preferable.
  • the molecular weight of the quaternary ammonium base having a linear alkyl group is preferably 200 or more and 700 or less. More preferably 400 or more and 600 or less.
  • the surface specific resistance value can be expressed, and furthermore, the suppression of migration to the back surface cannot be suppressed in a well-balanced manner.
  • the molecular weight is 700 or less, the surface specific resistance value can be expressed, and furthermore, the occurrence of aggregation due to interaction with the resin functional group can be suppressed during the preparation of the coating liquid.
  • At least one amide bond or urethane bond may be included between the linear alkyl chain and the quaternary ammonium base.
  • the urethane resin having a polycarbonate structure in the present invention preferably has a urethane bond partial structure derived from at least a polycarbonate polyol component and a polyisocyanate component, and further contains a chain extender as necessary. Furthermore, a polyisocyanate having a branched structure is synthesized and polymerized by the presence of 3 or more terminal functional groups in any of the raw materials constituting the molecular chain to form a branched molecular chain structure. It is preferably introduced by
  • the lower limit of the number of terminal functional groups in the molecular chain is preferably 3, more preferably 4, depending on the branched structure of the polycarbonate urethane resin and the urethane resin in the present invention when it has a branched structure. When the number is 3 or more, the blocking resistance when water is attached can be improved, which is preferable.
  • the upper limit of the number of terminal functional groups in the molecular chain of the urethane resin having a polycarbonate structure in the present invention is preferably 6 due to its branched structure. When the number is 6 or less, the resin can be stably dispersed in the aqueous solution, which is preferable.
  • the polycarbonate polyol component used for synthesizing and polymerizing the polycarbonate urethane resin in the present invention preferably contains an aliphatic polycarbonate polyol having excellent heat resistance and hydrolysis resistance.
  • Aliphatic polycarbonate polyols include aliphatic polycarbonate diols and aliphatic polycarbonate triols, and aliphatic polycarbonate diols can be preferably used.
  • Aliphatic polycarbonate diols used for synthesizing and polymerizing the urethane resin having a polycarbonate structure in the present invention include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 - diols such as pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol and dipropylene glycol; Aliphatic polycarbonate diols obtained by reacting one or more of them with, for example, carbonates such as dimethyl carbonate, ethylene carbonate and phosgene.
  • the number average molecular weight of the polycarbonate polyol in the present invention is preferably 1,000 to 3,000. More preferably 1200-2900, most preferably 1500-2800. When it is 1000 or more, the ink adhesion can be improved, which is preferable. When it is 3000 or less, it is preferable because the back migration of the antistatic agent can be suppressed.
  • polyisocyanate used for the synthesis and polymerization of the polycarbonate urethane resin in the present invention examples include aromatic-aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl ) Alicyclic diisocyanates such as cyclohexane, hexamethylene diisocyanate, and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, or these compounds are added singly or in combination with trimethylolpropane or the like in advance. and polyisocyanates.
  • aromatic-aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate
  • 1,3-bis(isocyanatomethyl ) Alicyclic
  • Chain extenders 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, and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water.
  • the polycarbonate polyol component, polyisocyanate, and chain extender are allowed to react at an appropriate temperature and time, and then trifunctional or higher hydroxyl groups or isocyanate groups are added.
  • a method of adding a compound having a compound and further advancing the reaction can be preferably employed.
  • compounds having a trifunctional or higher hydroxyl group include caprolactone triol, glycerol, trimethylolpropane, butanetriol, hexanetriol, 1,2,3-hexanetriol, 1,2,3-pentanetriol, 1,3 ,4-hexanetriol, 1,3,4-pentanetriol, 1,3,5-hexanetriol, 1,3,5-pentanetriol and polyethertriol.
  • the polyether triols include, for example, glycerin, alcohols such as trimethylolpropane, diethylenetriamine, and the like, using one or more compounds having three active hydrogens as initiators, ethylene oxide, propylene oxide, and butylene.
  • a specific example of the compound having a trifunctional or higher isocyanate group is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule.
  • trifunctional or higher isocyanate compounds are aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates having two isocyanate groups. and adducts.
  • Aromatic diisocyanates include, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate isocyanate, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.
  • Aliphatic diisocyanates are, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2, 4,4-trimethylhexamethylene diisocyanate and the like.
  • araliphatic diisocyanates include xylylene diisocyanate, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.
  • Alicyclic diisocyanates include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, and the like.
  • IPDI isophorone diisocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate
  • the burette body is a self-condensed product having a burette bond formed by self-condensation of an isocyanate monomer, and examples thereof include a burette body of hexamethylene diisocyanate.
  • a nurate compound is a trimer of an isocyanate monomer, and examples thereof include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a trimer of tolylene diisocyanate, and the like.
  • the adduct refers to a tri- or higher functional isocyanate compound obtained by reacting the above-mentioned isocyanate monomer with a tri- or higher-functional low-molecular-weight active hydrogen-containing compound, for example, a compound obtained by reacting trimethylolpropane and hexamethylene diisocyanate. , a compound obtained by reacting trimethylolpropane and tolylene diisocyanate, a compound obtained by reacting trimethylolpropane and xylylene diisocyanate, a compound obtained by reacting trimethylolpropane and isophorone diisocyanate, and the like.
  • chain extenders having a number of functional groups of 3 or more include trimethylolpropane and alcohols having a hydroxy group of 3 or more functional groups, such as pentaerythritol, which are described in the above description of chain extenders.
  • the easy-adhesion layer in the present invention is preferably provided by an in-line coating method, which will be described later, using a water-based coating liquid. Therefore, it is desirable that the urethane resin of the present invention has water solubility or water dispersibility.
  • water-soluble or water-dispersible means dispersing in water or an aqueous solution containing less than 50% by mass of a water-soluble organic solvent.
  • a sulfonic acid (salt) group or a carboxylic acid (salt) group can be introduced (copolymerized) into the urethane molecular skeleton.
  • a weakly acidic carboxylic acid (salt) group it is preferable to introduce a weakly acidic carboxylic acid (salt) group, and it is preferable to suppress the interaction (gelling) with the cationic antistatic agent.
  • nonionic groups such as polyoxyalkylene groups can also be introduced.
  • a polyol compound having a carboxylic acid group such as dimethylolpropanoic acid or dimethylolbutanoic acid is introduced as a copolymerization component to form a salt.
  • salt-forming agents include ammonia, trialkylamines such as trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine and tri-n-butylamine; -N-dialkylalkanolamines such as alkylmorpholines, N-dimethylethanolamine and N-diethylethanolamine. These can be used alone or in combination of two or more.
  • the composition molar ratio of the polyol compound having a carboxylic acid (salt) group in the urethane resin is When the total polyisocyanate component of is 100 mol %, the content is preferably 3 to 60 mol %, preferably 5 to 40 mol %. When the composition molar ratio is 3 mol % or more, water dispersibility is obtained, which is preferable. Further, when the composition molar ratio is 60 mol % or less, water resistance is maintained and moist heat resistance is obtained, which is preferable.
  • the urethane resin in the present invention may have a blocked isocyanate structure at the end to improve toughness.
  • a blocked isocyanate may be added as a cross-linking agent to the easily adhesive layer-forming composition.
  • Tri- or higher functional blocked isocyanates are more preferred, and tetra- or higher functional blocked isocyanates are particularly preferred. It is possible to control the antistatic property of the surface of the easily adhesive layer and to suppress the migration of the antistatic agent to the back by these.
  • the blocked isocyanate in the present invention can introduce a hydrophilic group into the precursor polyisocyanate to impart water solubility or water dispersibility.
  • Hydrophilic groups include (1) quaternary ammonium salts of dialkylaminoalcohols and quaternary ammonium salts of dialkylaminoalkylamines, etc., (2) sulfonates, carboxylates, phosphates, etc., and (3) alkyl groups. Polyethylene glycol, polypropylene glycol and the like with one end blocked can be mentioned. When a hydrophilic site is introduced, it becomes (1) cationic, (2) anionic, and (3) nonionic.
  • anionic and nonionic resins that are easily compatible with each other are preferable because many other water-soluble resins are anionic.
  • the anionic resin is excellent in compatibility with other resins, and the nonionic resin does not have an ionic hydrophilic group, so it is also preferable for improving the resistance to moist heat.
  • the anionic hydrophilic group preferably has a hydroxyl group for introduction into the polyisocyanate and a carboxylic acid group for imparting hydrophilicity.
  • a carboxylic acid group for imparting hydrophilicity.
  • examples include glycolic acid, lactic acid, tartaric acid, citric acid, oxybutyric acid, oxyvaleric acid, hydroxypivalic acid, dimethylolacetic acid, dimethylolpropanoic acid, dimethylolbutanoic acid, and polycaprolactone having a carboxylic acid group.
  • Organic amine compounds are preferred for neutralizing carboxylic acid groups.
  • ammonia methylamine, ethylamine, propylamine, isopropylamine, butylamine, 2-ethylhexylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine , linear, branched 1, 2 or tertiary amines having 1 to 20 carbon atoms such as ethylenediamine, cyclic amines such as morpholine, N-alkylmorpholine and pyridine, monoisopropanolamine, methylethanolamine, methylisopropanolamine, hydroxyl group-containing amines such as dimethylethanolamine, diisopropanolamine, diethanolamine, triethanolamine, diethylethanolamine and triethanolamine;
  • the nonionic hydrophilic group preferably has 3 to 50, more preferably 5 to 30 repeating units of ethylene oxide and/or propylene oxide of polyethylene glycol or polypropylene glycol blocked at one end with an alkyl group.
  • the repeating unit is too small, the compatibility with the resin is deteriorated, resulting in an increase in haze.
  • a nonionic, anionic, cationic, or amphoteric surfactant can be added to the blocked isocyanate of the present invention in order to improve water dispersibility.
  • nonionic compounds such as polyethylene glycol and polyhydric alcohol fatty acid esters; anionic compounds such as fatty acid salts, alkyl sulfates, alkylbenzenesulfonates, sulfosuccinates and alkylphosphates; cationic compounds such as alkylamine salts and alkylbetaines; Examples thereof include surfactants such as carboxylic acid amine salts, sulfonic acid amine salts, and sulfate ester salts.
  • water-soluble organic solvents can be contained in addition to water.
  • the organic solvent used in the reaction or it can be removed and another organic solvent can be added.
  • cross-linking agents include urea-based, epoxy-based, melamine-based, oxazoline-based, carbodiimide-based, and the like.
  • a catalyst or the like can be appropriately used as necessary in order to accelerate the cross-linking reaction.
  • the polyester resin used to form the easy-adhesion layer in the present invention may be a linear one, but is more preferably a polyester resin having a dicarboxylic acid and a diol having a branched structure as its constituent components.
  • the dicarboxylic acid referred to here is mainly composed of terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid, as well as aliphatic dicarboxylic acids such as adipic acid and sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 2, Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid are included.
  • a branched glycol is a diol having a branched alkyl group, such as 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2- Methyl-2-butyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n -hexyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl- 1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propane
  • the branched glycol component which is the more preferred embodiment, is contained in the total glycol component in a proportion of preferably 10 mol% or more, more preferably 20 mol% or more.
  • the upper limit of the glycol component in all glycol components is preferably 80 mol% or less, more preferably 70% by mass.
  • the concentration of the oligomer, which is a by-product, is suppressed, and the transparency of the easy-adhesion layer is favorable, which is preferable.
  • Ethylene glycol is most preferable as the glycol component other than the above compounds.
  • Diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol, or the like may be used in small amounts.
  • Terephthalic acid or isophthalic acid is most preferable as the dicarboxylic acid as a constituent of the polyester resin.
  • 5-sulfoisophthalic acid, 5-sodiumsulfoisophthalic acid and the like can be mentioned.
  • a polyester resin containing a dicarboxylic acid having a naphthalene skeleton may be used, but its quantitative ratio is 5 mol% or less in the total carboxylic acid component in order to suppress deterioration of adhesion to UV ink. is preferred and may not be used.
  • triol or tricarboxylic acid may be included to the extent that the properties of the polyester resin are not impaired.
  • the polyester resin may contain polar groups other than carboxyl groups.
  • sulfonic acid metal bases phosphoric acid groups, and the like can be mentioned, and one or more of these can be used.
  • a metal salt such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-[4-sulfophenoxy]isophthalic acid, or 2-sulfo-1
  • Dicarboxylic acids or glycols containing metal salts of 4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol, etc., containing sulfonic acid metal bases are used as polycarboxylic acid components or polyol components. 10 mol % or less, preferably 7 mol % or less, more preferably 5 mol % or less of the total of If it exceeds 10 mol %, the hydrolysis resistance
  • the resin solid content concentration in the coating liquid means the total solid content concentration of the polyester resin, the urethane resin having a polycarbonate structure, and the cross-linking agent. It is desirable to adjust the resin solid content concentration in the coating liquid to 5 to 17%. When the resin solid content concentration is 5% or more, the thickness of the easy-adhesion layer after drying and curing does not become too thin, and the easy-adhesion of UV-curable inks and the like is favorable, which is preferable. On the other hand, when the resin solid content concentration is 17% or less, sufficient crosslinkability can be obtained when the crosslinker is contained, and migration of the antistatic agent to other articles or the back surface can be suppressed, and blocking phenomenon can also occur. It is preferable because it can be suppressed.
  • the ion-conducting antistatic agent is contained in an amount of 1 to 8% by mass. If the specified range is satisfied, antistatic performance can be obtained. Furthermore, it is a preferable range because the antistatic component does not migrate to other articles or the back surface after heating and moist heat treatment.
  • the content of the urethane resin having a polycarbonate structure is 5 to 50% by mass when the total solid content of the polyester resin, the urethane resin having a polycarbonate structure, and the cross-linking agent is 100% by mass. Satisfying the above range is preferable because good affinity with various materials and UV inks can be achieved and adhesion can be achieved. If it is in the above-specified range, it is preferable because it has excellent adhesion and antistatic performance, and the antistatic agent can suppress migration to other articles or the back surface even under moist heat resistance.
  • the upper limit of the content of the cross-linking agent is preferably 50% by mass when the total of the solid content of the polyester resin, the urethane resin having a polycarbonate structure, and the cross-linking agent is 100% by mass.
  • the polyester resin content is preferably 10 to 70% by mass when the total solid mass of the polyester resin, the urethane resin having a polycarbonate structure, and the three cross-linking agents is 100% by mass.
  • additives such as surfactants, Ph adjusters, antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic Lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents and the like may be added.
  • the above surfactants are sometimes used in anticipation of effects such as solubilizing agents, dispersing agents, antifoaming agents, and wettability aids.
  • the hydrophilic part of the surfactant is divided into ionic (cationic, anionic, amphoteric) and nonionic.
  • ionic cationic, anionic, amphoteric
  • nonionic When used as a water-based coating material, a polyester film used as a substrate is used because of its low surface energy and poor wettability. Therefore, it is often used as a wettability aid for adjusting the surface tension of water-based coating materials.
  • the surfactant is preferably one that can lower the surface tension of the coating solution to 50 dyne/cm or less, preferably 40 dyne/cm or less, and promotes wetting of the polyester film.
  • Trimethylammonium salt dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, monoalkyl sulfate, alkylpolyoxyethylene sulfate, alkylbenzenesulfonate, monoalkylphosphate, alkyldimethylamine oxide, alkylcarboxybetaine, polyoxyethylene Alkyl ethers, fatty acid sorbitan esters, alkyl polyglucosides, fatty acid diethanolamides, alkyl monoglyceryl ethers, etc., among which polyether-modified silicones are preferred.
  • the amount of surfactant added is preferably 0.1% by mass or more and 1.0% by mass or less when the total solid mass in the coating liquid is 100% by mass. It is more preferably in the range of 0.2% by mass to 0.8% by mass. A content of 0.1% by mass or more is preferable because a wettability effect as a surfactant can be obtained. Moreover, when it is 1.0% by mass or less, the easy adhesion is maintained well, which is preferable.
  • a pH adjuster is used as the above additive.
  • Acids for adjusting the pH include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as oxalic acid, formic acid, citric acid and acetic acid. be done.
  • the pH is preferably in the range of pH 5 to 9, and more preferably in the range of pH 6 to 8.5. If the pH is 5 or less, the coating machine may be corroded, and the effect of accelerating the separation of the blocking agent when a blocked isocyanate is selected as the cross-linking agent is reduced. Moreover, if the pH is 9 or higher, the polyester resin used as the resin binder is hydrolyzed, which impairs adhesion and durability, which is not preferable.
  • Inert particles may be contained in the easy-adhesion layer in order to reduce the glossiness of the easy-adhesion layer surface.
  • the easy-adhesion layer can also contain lubricant particles in order to give the surface slipperiness, mattness, ink absorbency, and the like.
  • the particles may be inorganic particles or organic particles, and are not particularly limited, and include (1) silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, zirconium oxide, titanium dioxide, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium phosphate, magnesium hydroxide, barium sulfate, etc.
  • Inorganic particles (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene/acrylic, styrene/butadiene, polystyrene/acrylic, polystyrene/isoprene, polystyrene/isoprene, methyl methacrylate /Butyl methacrylate-based, melamine-based, polycarbonate-based, urea-based, epoxy-based, urethane-based, phenol-based, diallyl phthalate-based, polyester-based organic particles, etc., to give the easy-adhesion layer appropriate slipperiness.
  • Silica is particularly preferably used.
  • the average particle size of the inert particles is preferably 0.1 ⁇ m or more and 2.4 ⁇ m or less, more preferably 0.3 to 2.0 ⁇ m.
  • the average particle size of the inert particles is 0.04 ⁇ m or more, excessive increase in the glossiness of the film surface can be suppressed.
  • the particle size is 2.4 ⁇ m or less, it is possible to prevent the particles from falling off from the easy-adhesion layer, thereby avoiding powder falling off during various processes such as film running.
  • the average particle size can be determined as a result of morphological observation by a microscope using a scanning electron microscope, a transmission electron microscope, or the like. Specifically, the average value of the diameters of 20 arbitrarily selected particles in these microscopic observations is adopted.
  • the shape of the particles is not particularly limited as long as it satisfies the object of the present invention, and spherical particles and non-spherical irregular particles can be used.
  • the particle diameter of amorphous particles can be calculated as a circle equivalent diameter.
  • the circle-equivalent diameter is a value obtained by dividing the observed particle area by ⁇ , calculating the square root, and doubling the result.
  • the film is heated and stretched by a factor of 1.0 to 5.0 between two or multiple rolls having different circumferential speeds.
  • a heating means at this time a method using a heating roll or a method using a non-contact heating medium may be used, and these may be used in combination. A range is preferred.
  • the uniaxially stretched film is introduced into a tenter and stretched 1.0 to 6.0 times in the width direction at a temperature of (Tg-10°C) to Tm-10°C to obtain a biaxially stretched film.
  • Tg is the glass transition temperature of the polyester resin
  • Tm is the melting point of the polyester.
  • the film obtained as described above is preferably subjected to heat treatment as necessary, and the treatment temperature is preferably in the range of (Tm-60° C.) to Tm.
  • the easy-adhesion layer can be provided after the film is manufactured or during the manufacturing process.
  • any known method can be used for applying this coating liquid to the polyester film.
  • reverse roll coating method gravure coating method, kiss coating method, die coater method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, curtain coating method, etc. be done. These methods can be applied singly or in combination.
  • the thickness of the easy-adhesion layer can be appropriately set within the range of 0.001 to 2.00 ⁇ m.
  • the range is preferably 0.01 to 1.00 ⁇ m, more preferably 0.02 to 0.80 ⁇ m, still more preferably 0.05 to 0.50 ⁇ m, in order to achieve both workability and adhesiveness. It is preferable that the thickness of the easy adhesion layer is 0.001 ⁇ m or more because the adhesion is good.
  • the thickness of the easy-adhesion layer is 2.00 ⁇ m or less, the transfer of the antistatic agent to other articles or back surface can be suppressed, which is preferable.
  • the void-containing polyester film in the present invention preferably has an optical density (OD value) of 0.55 or more, more preferably 0.6 or more.
  • OD value optical density
  • the upper limit of the OD value is preferably 1.5. When it is 1.5 or less, sufficient whiteness can be exhibited without saturating the whiteness, which is preferable in terms of cost.
  • the OD value is a value in terms of a thickness of 50 ⁇ m, which is obtained by the measurement method described in the evaluation method described later.
  • the void-containing polyester film of the present invention preferably has a color tone b value of 4.0 or less, more preferably 3.0 or less.
  • a color tone b value of 4.0 or less, more preferably 3.0 or less.
  • the lower limit of the color tone b value is preferably ⁇ 5.0.
  • the film can be prevented from becoming bluish, and the resolution can be well balanced when used as a printing base material.
  • the void-containing polyester film of the present invention has a deflection of 100 mm or less and 60 mm or more due to its own weight of a sample with a length of 130 mm.
  • a film that can be used as a label without distortion can be achieved. If it is 100 mm or less, sufficient rigidity can be maintained, and the label can be kept upright even after being attached to the product, and the label can be given an excellent appearance. For example, wrinkles can be avoided when the label is sent out, and problems such as dents and distortions can be avoided when the label is wrapped around the product without being significantly affected by unevenness of the product.
  • self-weight deflection is 60 mm or more, it is possible to avoid an excessive increase in rigidity, avoid an increase in stress applied to the adhesive part when wrapped around a product, and suppress the tendency of the adhesive to come off. Therefore, it is important that self-weight deflection is within an appropriate range. Self-weight deflection can be effectively adjusted by specific gravity, thickness, and elastic modulus in the direction of deflection.
  • the thickness of the void-containing polyester film of the present invention is arbitrary, it is preferably 20 to 300 ⁇ m, more preferably 50 to 120 ⁇ m.
  • the thickness has a large effect on the amount of deflection due to its own weight. By increasing the thickness, it is possible to give the film bending rigidity and reduce the amount of deflection due to its own weight. It becomes small and the handling property as a label deteriorates.
  • the void-containing polyester film of the present invention preferably has a modulus of elasticity in the direction of deflection of 2500 MPa or more, more preferably 3500 MPa or more, depending on the thickness of the film.
  • the elastic modulus is 2500 MPa or more, it is possible to suppress the occurrence of wrinkles when feeding the roll label. Even if the thickness of the film cannot be increased, it is possible to adjust the film to have an appropriate self-weight deflection amount by increasing the elastic modulus.
  • the elastic modulus can be effectively adjusted by stretching ratios in the longitudinal direction and the width direction, and heat treatment conditions.
  • the void-containing polyester film of the present invention preferably has an apparent density of 0.8 g/cm 3 or more and 1.3 g/cm 3 or less, more preferably 0.90 g/cm 3 or more and 1.2 g/cm 3 or less. .
  • the apparent density is 0.8 g/cm 3 or more, it is possible to suppress an excessive increase in the number of cavities, and it is possible to exhibit light controllability during post-processing such as printing and during use. If it is 1.3 g/cm 3 or less, sufficient lightness and cushioning properties can be obtained.
  • the apparent density is a value obtained by the measurement method described in the evaluation method described later.
  • the present invention can be recovered and used as a recycled polyester feedstock, eg, to form films from the recycled feedstock.
  • Optical density It was measured using a transmission densitometer “Ihac-T5 type” manufactured by Ihara Denshi Kogyo Co., Ltd. and converted to a film thickness of 50 ⁇ m. It should be noted that the higher the optical density, the higher the hiding power.
  • Color tone b value was measured according to JIS-8722 using a Nippon Denshoku color difference meter (ZE6000) and converted to a film thickness of 50 ⁇ m. It was judged that the smaller the b value, the higher the whiteness and the weaker the yellowness.
  • a 24 mm wide and 50 mm long piece was cut out and completely adhered to the surface of the ink layer with a handy rubber roller so as not to mix air. Thereafter, the adhesive cellophane tape was peeled off vertically, and the remaining area of the printed layer was observed in an area of 24 mm ⁇ 50 mm, and judged according to the following criteria.
  • x Remaining area of the printed layer was less than 90% of the whole, and was regarded as unsatisfactory.
  • (Cationic antistatic agent) 116 g of N,N-dimethyl-1,3-propanediamine and 285 g of stearic acid having 17 carbon atoms were subjected to an esterification reaction at 100° C. under a nitrogen atmosphere for 10 hours, and tetrahydrofuran was added as a quaternization solvent to obtain the target amine. A specified amount of dimethyl sulfate was added to the solution, and the mixture was reacted at 70° C. for about 10 hours.
  • polyester resin 194.2 parts by weight of dimethyl terephthalate, 184.5 parts by weight of dimethyl isophthalate, 14.8 parts by weight of dimethyl-5-sodium sulfoisophthalate were added to a stainless steel autoclave equipped with an agitator, thermometer, and partial reflux condenser. , 185 parts by mass of neopentyl glycol, 188 parts by mass of ethylene glycol, and 0.2 parts by mass of tetra-n-butyl titanate were charged, and transesterification was carried out at a temperature of 160° C. to 220° C. for 4 hours.
  • the temperature was raised to 255° C., and the pressure in the reaction system was gradually reduced, followed by reaction under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin.
  • the resulting copolymerized polyester resin was pale yellow and transparent.
  • the reduced viscosity of the copolymerized polyester resin was measured, it was 0.40 dl/g.
  • the glass transition temperature by DSC was 65°C.
  • titanium oxide master pellets (M1) A mixture of 50% by mass of polyethylene terephthalate resin having a melt viscosity of 200 Pa ⁇ s and 50% by mass of anatase-type titanium dioxide having an average particle size of 0.3 ⁇ m (electron microscope method) is supplied to a vented twin-screw extruder and kneaded. A titanium oxide-containing master pellet (M1) was produced.
  • the solid content in the coating liquid of the compound constituting the coating layer is as follows. [Structure of Coating Layer (Coating Liquid A)] The total solid content contained in the coating layer is defined as 100% by mass.
  • - Cationic antistatic agent 6.2% by mass
  • ⁇ Urethane resin having a polycarbonate structure 25.5% by mass
  • ⁇ Blocked isocyanate cross-linking agent 10.9% by mass
  • ⁇ Polyester resin 54.6% by mass
  • ⁇ Silicone-based surfactant 0.4% by mass ⁇ pH adjuster (sodium hydrogen carbonate): 2.4% by mass
  • the solid content mass ratio of urethane resin/crosslinking agent/polyester resin is 28/12/60.
  • the unstretched film a was uniformly heated to 70° C. using heating rolls and longitudinally stretched by 1.4 times between two pairs of nip rolls having different circumferential speeds.
  • an infrared heater (rated 20 W/cm) equipped with a gold reflective film was installed in the middle of the nip rolls so as to face both sides of the film at a distance of 1 cm from the film surface. and heated.
  • the film was coated by the reverse gravure coating method using the coating composition described above so that the WET coating amount was 7 g/m 2 , and then introduced into a tenter at 140°C.
  • Example 1 The film was heated to 4.0 times in the transverse direction, fixed in width, subjected to heat setting treatment at 240°C, and further relaxed at 210°C in the width direction by 3% to obtain a void-containing polyester film with a thickness of 50 ⁇ m. (B/A/B).
  • the evaluation results of Example 1 are also shown in Table 1.
  • Table 1 the film of Example 1 used raw material resins satisfying the above requirements ( 1 ) to (3).
  • Example 2 A void-containing polyester film with a thickness of 50 ⁇ m was obtained in the same manner as in Example 1, except that the addition amount of the polypropylene resin in the unstretched film was 30% by mass and the transverse stretching ratio was 3.8 times.
  • Example 3 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1, except that the longitudinal draw ratio was 3.2 times.
  • Example 4 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 3, except that the solid components of the compound constituting the coating layer were changed as follows. [Structure of Coating Layer (Coating Liquid B)] The total solid content contained in the coating layer is defined as 100% by mass.
  • - Cationic antistatic agent 6.2% by mass ⁇ Urethane resin having a polycarbonate structure: 36.4% by mass ⁇ Blocked isocyanate cross-linking agent: 0% by mass ⁇ Polyester resin: 54.6% by mass ⁇ Silicone-based surfactant: 0.4% by mass ⁇ pH adjuster (sodium hydrogen carbonate): 2.4% by mass
  • the solid content mass ratio of urethane resin/crosslinking agent/polyester resin is 40/0/60.
  • Example 5 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 3, except that the addition amount of the polypropylene resin in the unstretched film was changed to 15% by mass.
  • Example 6 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 3, except that the amount of the polypropylene resin added to the unstretched film was changed to 30% by mass.
  • Example 7 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1, except that the transverse draw ratio was 3.8 times.
  • Example 8 As in Example 3, a void-containing polyester film having a thickness of 100 ⁇ m was obtained.
  • Example 9 A void-containing polyester film having a thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was 2.5 times and the transverse draw ratio was 2.5 times.
  • Example 10 A void-containing polyester film having a thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the addition amount of the polypropylene resin in the unstretched film was 15 mass % and the longitudinal stretching ratio was 3.5 times.
  • Example 11 A void-containing polyester film having a thickness of 100 ⁇ m was obtained in the same manner as in Example 3, except that the amount of the polypropylene resin added to the unstretched film was changed to 30% by mass.
  • Example 1 A void-containing polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1, except that the transverse draw ratio was 3.8 times.
  • Example 2 A void-containing polyester film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1, except that the longitudinal draw ratio was 3.2 times and the transverse draw ratio was 4.0 times.
  • Example 4 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was 2.5 times and the transverse draw ratio was 2.5 times.
  • Example 5 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 3, except that the solid components of the compound constituting the coating layer were changed as follows. [Structure of Coating Layer (Coating Liquid C)] The total solid content contained in the coating layer is defined as 100% by mass.
  • ⁇ Cationic antistatic agent 0% by mass ⁇ Urethane resin having a polycarbonate structure: 27.2% by mass ⁇ Blocked isocyanate cross-linking agent: 11.6% by mass ⁇ Polyester resin: 58.2% by mass ⁇ Silicone-based surfactant: 0.4% by mass ⁇ pH adjuster (sodium hydrogen carbonate): 2.6% by mass
  • the solid content mass ratio of urethane resin/crosslinking agent/polyester resin is 28/12/60.
  • Example 6 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 3, except that the solid components of the compound constituting the coating layer were changed as follows. [Structure of Coating Layer (Coating Liquid D)] The total solid content contained in the coating layer is defined as 100% by mass.
  • - Cationic antistatic agent 6.2% by mass ⁇ Urethane resin having a polycarbonate structure: 0% by mass ⁇ Blocked isocyanate cross-linking agent: 36.4% by mass ⁇ Polyester resin: 54.6% by mass ⁇ Silicone-based surfactant: 0.4% by mass ⁇ pH adjuster (sodium hydrogen carbonate): 2.6% by mass
  • the solid content mass ratio of urethane resin/crosslinking agent/polyester resin is 0/40/60.
  • Example 7 A void-containing polyester film having a thickness of 75 ⁇ m was obtained in the same manner as in Example 3, except that the solid components of the compound constituting the coating layer were changed as follows. [Structure of Coating Layer (Coating Liquid E)] The total solid content contained in the coating layer is defined as 100% by mass.
  • - Cationic antistatic agent 6.2% by mass ⁇ Urethane resin having a polycarbonate structure: 63.7% by mass ⁇ Blocked isocyanate cross-linking agent: 27.3% by mass ⁇ Polyester resin: 0% by mass ⁇ Silicone-based surfactant: 0.4% by mass ⁇ pH adjuster (sodium hydrogen carbonate): 2.6% by mass
  • the solid content mass ratio of urethane resin/crosslinking agent/polyester resin is 70/30/0.
  • Example 8 A void-containing polyester film having a thickness of 100 ⁇ m was obtained in the same manner as in Example 1, except that the transverse draw ratio was 3.8 times.
  • Example 9 A void-containing polyester film having a thickness of 100 ⁇ m was obtained in the same manner as in Example 1, except that the longitudinal draw ratio was 3.5 times.
  • Comparative Examples 1 to 4 the amount of deflection was outside the scope of the present invention, and wrinkles and adhesion peeling occurred.
  • Comparative Examples 5 to 7 the surface specific resistance values were outside the range of the present invention, and dust was adsorbed due to static electricity during printing, resulting in poor print quality. Furthermore, in Comparative Examples 8 and 9, the amount of deflection was outside the scope of the present invention, and adhesion peeling occurred.
  • a cavity-containing polyester that is excellent in lightness and cushioning properties, has good hiding properties, whiteness, thermal dimensional stability, and film-forming properties. system films can be provided.

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