WO2024042879A1 - Void-containing polyester-based easy adhesion film - Google Patents

Void-containing polyester-based easy adhesion film Download PDF

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Publication number
WO2024042879A1
WO2024042879A1 PCT/JP2023/024899 JP2023024899W WO2024042879A1 WO 2024042879 A1 WO2024042879 A1 WO 2024042879A1 JP 2023024899 W JP2023024899 W JP 2023024899W WO 2024042879 A1 WO2024042879 A1 WO 2024042879A1
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WIPO (PCT)
Prior art keywords
cavity
layer
polyester
resin
adhesive film
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PCT/JP2023/024899
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French (fr)
Japanese (ja)
Inventor
栄二 熊谷
豪 太田
功 瀧井
正太郎 西尾
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東洋紡株式会社
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Publication of WO2024042879A1 publication Critical patent/WO2024042879A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—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
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material

Definitions

  • the present invention relates to a cavity-containing polyester-based easily adhesive film containing cavities inside.
  • a known method for obtaining a film with functions similar to paper is to include a large amount of fine cavities inside the film.
  • This method involves mixing an incompatible thermoplastic resin (hereinafter referred to as an incompatible resin) in a polyester resin to obtain a sheet in which the incompatible resin is dispersed in the polyester resin. Stretch. Accordingly, this method causes cavities to develop due to interfacial peeling between the polyester resin and the incompatible resin.
  • incompatible resins for example, polyolefin resins such as polyethylene resin, polypropylene resin, and polymethylpentene resin (see, for example, Patent Documents 1 to 3) and polystyrene resins (see, for example, Patent Documents 4 and 5) have been proposed. ing.
  • polypropylene resin is excellent in terms of cavity development and cost performance.
  • the purpose of the present invention is to improve the above-mentioned problems of the prior art, and to achieve excellent lightness, film-forming properties, hiding properties, whiteness, and easy adhesion even when polypropylene resin is mainly used as a cavity developing agent.
  • An object of the present invention is to provide a hollow-containing polyester-based easily adhesive film.
  • the present inventors discovered the following by adding a very small amount of silicone resin to polypropylene resin. That is, the present inventors have found that it is possible to improve the heat resistance of polypropylene dispersed particles in a polyester resin, and to reduce the deformation of the polypropylene dispersed particles during heat stretching and heat setting. As a result, the present inventors found that a hollow polyester-based easily adhesive film having excellent lightness, film-forming properties, concealing properties, and whiteness can be obtained. Furthermore, the present inventors have discovered a cavity-containing polyester-based easily adhesive film that can suppress deterioration in coatability and printability, which are side effects of silicone resins, by adjusting the laminated structure and the amount of silicone resin added.
  • the cavity-containing polyester easily adhesive film of the present invention has the following configuration.
  • a first coating layer B1 containing a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a second coating layer B2 containing a polyester resin containing an inorganic pigment are laminated in this order.
  • a functional adhesive layer is provided on the first coating layer B1
  • the apparent density is 0.80 g/cm 3 or more and 1.20 g/cm 3 or less
  • a cavity-containing polyester-based easily adhesive film in which the cavity-containing layer A includes a composition containing a polyester resin, a polypropylene resin, and a silicone resin.
  • the cavity-containing polyester easily adhesive film according to the above-mentioned item 1, wherein in the cavity-containing layer A, the content of polydimethylsiloxane in the silicone resin is 1 ppm or more and 2,500 ppm or less based on the total mass of the cavity-containing layer A. 3. In the cavity-containing layer A, the cavity-containing polyester according to the first aspect, wherein the content of polydimethylsiloxane in the silicone resin is 0.005% by mass or more and 2.000% by mass or less based on 100% by mass of the polypropylene resin. Easy adhesive film. 4. 1. The cavity-containing polyester-based easily adhesive film according to the above 1, wherein the inorganic pigment in the first coating layer B1 and the second coating layer B2 is titanium oxide. 5.
  • the ratio of the sum of the thicknesses of the first coating layer B1 and the second coating layer B2 to the sum of the thickness of the first coating layer B1, the thickness of the cavity-containing layer A, and the thickness of the second coating layer B2 is , 6% or more and 40% or less, the void-containing polyester easily adhesive film according to the above-mentioned item 1.
  • the cavity-containing polyester easily adhesive film according to the above-mentioned item 1 which has a total light transmittance of 1% or more and 30% or less.
  • the adhesion remaining area is based on the following evaluation method.
  • UV ink manufactured by T&K TOKA Co., Ltd., product name "BEST CURE (registered trademark) UV161 Indigo S”
  • a printing machine made by T&K TOKA Co., Ltd.
  • 10. 1 The cavity-containing polyester-based easy-adhesion film according to the above-mentioned item 1, wherein the number of pinhole-like repellents in the functional easy-adhesion layer is 5 pieces/m 2 or less. (However, the number of pinhole repellents in the functional adhesive layer is evaluated by visually observing the functional adhesive layer of the hollow polyester adhesive film under a three-wavelength fluorescent lamp and counting the number of pinhole repellents. ) 11.
  • 11. The cavity-containing polyester easily adhesive film according to any one of the above items 1 to 10, which is used for labels, cards, packaging materials, or release films.
  • the present invention provides a cavity-containing polyester-based easily adhesive film that has excellent lightness, film-forming properties, hiding properties, whiteness, and adhesion to various inks even when it mainly contains polypropylene resin as a cavity developer. can.
  • the cavity-containing polyester-based easily adhesive film of the present invention comprises a first coating layer B1 made of a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a first coating layer B1 made of a polyester resin containing an inorganic pigment. It is preferable that the two coating layers B2 and B2 are laminated in this order.
  • This cavity-containing layer A is preferably made of a composition containing a polyester resin, a polypropylene resin, and a silicone resin. Further, the apparent density of this hollow-containing polyester-based easily adhesive film is preferably 0.80 g/cm 3 or more and 1.20 g/cm 3 or less.
  • the polyester resin that is the main component of the cavity-containing layer A, the first coating layer B1, and the second coating layer B2 is a polymer synthesized from dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative. is preferred.
  • Typical examples of such polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate. Among these, polyethylene terephthalate is preferred from the viewpoint of mechanical properties, heat resistance, cost, and the like.
  • the copolymerization component includes dicarboxylic acid components such as isophthalic acid, naphthalene dicarboxylic 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 repeating unit.
  • a method for producing a polyester resin for example, it is preferable to first use the above-mentioned dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative as the main starting materials. Next, it is preferable to carry out an esterification or transesterification reaction according to a conventional method, followed by a polycondensation reaction at high temperature and reduced pressure.
  • the intrinsic viscosity of the polyester resin is preferably 0.50 dl/g or more and 0.9 dl/g or less, more preferably 0.55 dl/g or more and 0.85 dl/g or less, from the viewpoint of film formability, recovery and utilization, etc. .
  • the content of the polyester resin is preferably 70% by mass or more and 97% by mass or less, and more preferably 75% by mass or more and 95% by mass or less, based on a total of 100% by mass of all components contained in the cavity-containing layer A.
  • the content of the polyester resin is 70% by mass or more, the cavity-containing polyester-based easily adhesive film can suppress deterioration in film formability.
  • the content of polyester resin is 97% or less, cavities can be formed in the cavity-containing polyester-based easily adhesive film by adding polypropylene resin and silicone resin.
  • the cavity-containing polyester-based easily adhesive film of the present invention can maintain cavity development by adopting a specific layer structure and using a specific polypropylene resin.
  • the cavity-containing polyester easily adhesive film of the present invention has sufficient lightness and cushioning properties, as well as excellent film formability and concealment properties. and excellent whiteness.
  • the polypropylene resin used in the present invention is preferably a crystalline polypropylene having propylene units of 95 mol% or more, more preferably 98 mol% or more. Particularly preferred is a crystalline polypropylene homopolymer containing 100 mol% of propylene units.
  • the polypropylene resin used in the present invention preferably has a melt flow rate (MFR) of 1.0 g/10 minutes to 10.0 g/10 minutes, and 1.5 g/10 minutes from the viewpoint of cavity development and film forming properties. It is more preferably 7.0 g/min or less. If the MFR is 1.0 g/10 minutes or more and 10.0 g/10 minutes or less, the polypropylene dispersed particles will be difficult to deform when extruded from the die, making it easier to form cavities. Furthermore, when the MFR is 1.0 g/10 minutes or more and 10.0 g/10 minutes or less, the dispersibility of the polypropylene dispersed particles is excellent, sufficient hiding properties are obtained, and film forming properties are also excellent. Note that the melt flow rate (MFR) is a value measured under the conditions of 230° C. and a load of 2.16 kg according to JIS K 7210.
  • the deflection temperature under load is preferably 85°C or higher, more preferably 90°C or higher, and even more preferably 95°C or higher.
  • the upper limit is not particularly limited, but is preferably 135°C or lower.
  • the deflection temperature under load is 85° C. or higher, the polypropylene dispersed particles become difficult to collapse, making it easier to form cavities, especially in the longitudinal stretching process in which the film is stretched by heating at a temperature higher than the glass transition temperature of the polyester resin, which will be described later.
  • the deflection temperature under load is a value measured when the bending stress of the test piece is 0.45 MPa according to method B of JIS K 7191-1, 2.
  • the weight average molecular weight (Mw) of the polypropylene resin used in the present invention is preferably 200,000 or more and 450,000 or less, more preferably 250,000 or more and 400,000 or less, from the viewpoint of cavity development and suppressing thermal deterioration in the extrusion process and recovery process.
  • Mw is 450,000 or less
  • the dispersibility of the polypropylene dispersed particles is improved, sufficient hiding properties are obtained, and film forming properties are excellent.
  • Mw is 200,000 or more, the polypropylene dispersed particles become difficult to deform, making it easier to form cavities.
  • Mw is 200,000 or more, it is preferable because it is possible to suppress a decrease in cavity development even when recovered raw materials are used.
  • the molecular weight distribution (Mw/Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), is preferably 2 or more and 6 or less, and more preferably 2 or more and 5 or less.
  • Mw/Mn is an index representing the spread of molecular weight distribution, and the larger this value is, the wider the molecular weight distribution is.
  • Mw/Mn is 6 or less, low molecular weight components are reduced, so even when recycled raw materials are used, reduction in whiteness and cavity development can be suppressed, which is preferable.
  • Mw/Mn is 2 or more, it is suitable for industrial production from a cost standpoint.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC).
  • the content of the polypropylene resin is preferably 3% by mass or more and 30% by mass or less, and 5% by mass or less, based on the total 100% by mass of all components contained in the cavity-containing layer A. % or more and 25% by mass or less is more preferable.
  • the content of the polypropylene resin is 3% by mass or more and 30% by mass or less, cavities can be formed to obtain sufficient lightness and cushioning properties, and the film-forming properties are excellent.
  • silicone resin used in the present invention examples include silicone polymers, such as partially crosslinked silicone polymers (i.e., silicone resins that are silicone resins in the narrow sense) and linear silicone polymers (i.e., silicone rubber). It will be done. Specific examples include methyl silicone resin, methylphenyl silicone resin, phenyl silicone resin, alkyd-modified silicone resin, polyester-modified silicone resin, urethane-modified silicone resin, epoxy-modified silicone resin, and acrylic-modified silicone resin. A silicone resin having a crosslinked structure is preferred from the viewpoint of being able to withstand the extrusion temperature of the polyester resin that is the base resin and suppressing process contamination due to sublimation.
  • silicone polymers such as partially crosslinked silicone polymers (i.e., silicone resins that are silicone resins in the narrow sense) and linear silicone polymers (i.e., silicone rubber). It will be done. Specific examples include methyl silicone resin, methylphenyl silicone resin, phenyl silicone resin, alkyd-modified silicone resin, polyester-
  • the method of adding the silicone resin is not particularly limited, but it may be directly added by dry blending a powder or pellet with the base resin.
  • a masterbatch may be prepared in advance by melt-mixing polyester resin, polypropylene resin, and silicone resin.
  • the amount of silicone resin added is preferably 1 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 8,000 ppm or less, based on the total mass of the cavity-containing layer A, from the viewpoint of cavity development, film formability, and manufacturing cost.
  • the amount of silicone resin added is preferably 1 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 8,000 ppm or less, based on the total mass of the cavity-containing layer A, from the viewpoint of cavity development, film formability, and manufacturing cost.
  • the content of polydimethylsiloxane derived from silicone resin is determined by NMR (nuclear magnetic resonance) method.
  • the content of polydimethylsiloxane derived from silicone resin is preferably 1 ppm or more and 2,500 ppm or less, more preferably 100 ppm or more and 2,400 ppm or less, based on the total mass of the cavity-containing layer A, from the viewpoint of cavity development, film formability, and manufacturing cost. preferable. Even more preferably 100 ppm or more and 1400 ppm or less.
  • the apparent density can be efficiently lowered.
  • By controlling the content to 2500 ppm or less it is possible to suppress process contamination and deterioration of film formability.
  • silicone resin has a crosslinked structure and is insoluble in solvents
  • the content of polydimethylsiloxane present in the silicone resin can be determined using the NMR measurement method described later. It can be used as an index of resin content.
  • the content of polydimethylsiloxane in the silicone resin contained in the cavity-containing layer A determined by the NMR method is 0.005% by mass or more and 2.000% by mass or less based on 100% by mass of the polypropylene resin in the cavity-containing layer A. It is preferable that More preferably 0.010% by mass or more and 1.800% by mass or less. Even more preferably 0.100% by mass or more and 0.800% by mass or less.
  • the heat resistance of the polypropylene resin is improved, and cavities can be efficiently developed without being crushed during stretching.
  • deterioration in film formability can be suppressed.
  • the cavity-containing layer A By containing a trace amount of silicone resin in the cavity-containing layer A, heat resistance can be imparted to the polypropylene resin. Therefore, it is possible to suppress thermal deterioration of the polypropylene resin during material recycling, and it has the effect of maintaining cavity development. Even in the case of a cavity-containing polyester-based easily adhesive film, the cavities are less likely to collapse in a high-temperature environment, so it is possible to suppress thickness unevenness caused by local collapse of the polypropylene resin, which is a void generator.
  • incompatible resins other than polypropylene resin may be contained within a range that does not impair the purpose of the present invention.
  • the content of the polypropylene resin is preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass, based on the total 100% by mass of the incompatible resins in the cavity-containing layer A.
  • a dispersant such as polyethylene glycol or a surfactant.
  • these polyester resins or polypropylene resins may contain small amounts of other polymers, antioxidants, heat stabilizers, matting agents, pigments, ultraviolet absorbers, and fluorescent enhancers.
  • a whitening agent, a plasticizer, or other additives may also be contained.
  • an antioxidant or a heat stabilizer in order to suppress oxidative deterioration of the polypropylene resin, it is preferable to include an antioxidant or a heat stabilizer.
  • the types of antioxidants and heat stabilizers are not particularly limited, but include, for example, hindered phenol type, phosphorus type, hindered amine type, etc., and these may be used alone or in combination.
  • the amount added is preferably 1 ppm or more and 50,000 ppm or less based on the total mass of the cavity-containing layer A.
  • excellent whiteness can be ensured even without adding a fluorescent brightener to the cavity-containing layer A.
  • an inorganic pigment can be contained in the polyester resin or polypropylene resin as necessary in the hollow polyester-based easy-adhesive film in order to improve hiding properties and whiteness.
  • inorganic pigments include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, titanium oxide, and zinc sulfide.
  • titanium oxide, calcium carbonate, and barium sulfate are preferred from the viewpoint of hiding power and whiteness.
  • these inorganic pigments may be used alone or in combination of two or more. These inorganic pigments can be incorporated into the cavity-containing polyester-based easily adhesive film by adding them to the polyester resin or polypropylene resin in advance.
  • the method of mixing the inorganic pigment with the polyester resin or polypropylene resin is not particularly limited, but the following method may be mentioned. Namely, there are methods such as dry blending polyester resin and polypropylene resin and then feeding them directly into a film forming machine, dry blending polyester resin and polypropylene resin, and then melt-kneading them using various general kneading machines to form a masterbatch. can be mentioned.
  • the cavity-containing polyester-based easily adhesive film of the present invention comprises a first coating layer B1 made of a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a first coating layer B1 made of a polyester resin containing an inorganic pigment. It has a laminated structure in which two coating layers B2 are laminated in this order.
  • the cavity-containing layer A containing the polypropylene resin is exposed to the surface layer, some of the exposed polypropylene dispersed particles will cause process contamination such as roll stains.
  • the first coating layer B1 and the second coating layer B2 containing an inorganic pigment cover the cavity-containing layer A, thereby having the effect of preventing a decrease in whiteness.
  • the ratio of the total thickness of the first coating layer B1 and the second coating layer B2 to the sum of the thickness of the first coating layer B1, the thickness of the cavity-containing layer A, and the thickness of the second coating layer B2 (hereinafter referred to as layer ratio) ) is preferably 6% or more and 40% or less, more preferably 8% or more and 30% or less, from the viewpoint of cavity development and suppression of exposure of the polypropylene resin and silicone resin.
  • the layer ratio is 6% or more and 40% or less, exposure of the polypropylene resin and silicone resin can be suppressed, and the contact angle of water and the contact angle of diiodomethane can be reduced.
  • the layer ratio is 6% or more and 40% or less, it is easy to form cavities for obtaining sufficient light weight and cushioning properties.
  • Examples of the inorganic pigments contained in the first coating layer B1 and the second coating layer B2 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 from the viewpoint of hiding power and whiteness, and titanium oxide is particularly preferred.
  • these inorganic pigments may be used alone or in combination of two or more. These pigments can be incorporated into the film by adding them to the polyester resin in advance.
  • the amount of the inorganic pigment added in the first coating layer B1 is not particularly limited, but is preferably 1% by mass or more and 35% by mass or less, more preferably It is 2% by mass or more and 30% by mass or less.
  • the amount of the inorganic pigment added is 1% by mass or more and 35% by mass or less, it is easy to improve the hiding property and whiteness of the hollow polyester adhesive film, and the production of the hollow polyester adhesive film is easy. Film properties and mechanical strength can be improved.
  • the amount of the inorganic pigment added in the second coating layer B2 is not particularly limited, but it is preferably the same as the amount of the inorganic pigment added in the first coating layer B1. It is also preferable that the first coating layer B1 and the second coating layer B2 are substantially the same in composition, thickness, and the like. That is, it is also preferable that the laminated structure of the first coating layer B1/cavity-containing layer A/second coating layer B2 is a two-type, three-layer structure. It is preferable that a functional adhesive layer is laminated on the first coating layer B1, and the second coating layer B2 has the same composition or thickness as the functional adhesive layer on the first coating layer B1. It is also preferable that functional adhesion layers having different values are laminated.
  • the inorganic pigment contained in the first coating layer B1 and the second coating layer B2 is preferably in the form of particles, and the average particle diameter of the particles is preferably 0.1 to 4.0 ⁇ m, particularly preferably It is 0.3 to 1.5 ⁇ m.
  • particulate white pigments such as titanium oxide, barium sulfate, calcium carbonate, and zinc sulfide are preferred, and these may be mixed.
  • the shape of the particles is not particularly limited as long as the object of the present invention is met, and spherical particles and irregularly shaped non-spherical particles can be used.
  • the particle diameter of irregularly shaped particles can be calculated as a circular equivalent diameter.
  • the cavity-containing polyester-based easy-adhesive film of the present invention has functionality that combines easy-adhesion and antistatic properties on at least one side of the film in order to improve the applicability and adhesion of printing inks and coating agents. It is preferable to provide an easily adhesive layer.
  • the resin to be included in the composition constituting the functional adhesive layer includes polyester resin, urethane resin having a polycarbonate structure, polyester urethane resin, acrylic resin, etc. Disclosed as a means for improving the adhesion of ordinary polyester films. Compounds that have the following properties are applicable. In order to facilitate so-called in-line coating, the resin is preferably water-soluble or water-dispersible.
  • a blocked isocyanate may be added as a crosslinking agent to the composition constituting the functional adhesive layer.
  • Trifunctional or higher functional block isocyanates are more preferred, and tetrafunctional or higher functional block isocyanates are particularly preferred.
  • a hydrophilic group can be introduced into the precursor polyisocyanate.
  • Hydrophilic groups include (1) quaternary ammonium salts of dialkylamino alcohols and quaternary ammonium salts of dialkylaminoalkylamines, (2) sulfonates, carboxylates, phosphates, etc., and (3) alkyl groups. Examples include polyethylene glycol and polypropylene glycol with one end blocked.
  • a hydrophilic site When a hydrophilic site is introduced, it becomes (1) cationic, (2) anionic, and (3) nonionic.
  • anionic resins since many other water-soluble resins are anionic, anionic or nonionic resins that are easily compatible are preferred. Furthermore, anionic resins have excellent compatibility with other resins, and nonionic resins do not have ionic hydrophilic groups, so they are preferable for improving moist heat resistance.
  • anionic hydrophilic group those having a hydroxyl group for introduction into the polyisocyanate and a carboxylic acid group for imparting hydrophilicity are preferred.
  • examples include glycolic acid, lactic acid, tartaric acid, citric acid, oxybutyric acid, oxyvaleric acid, hydroxypivalic acid, dimethylolacetic acid, dimethylolpropanoic acid, dimethylolbutanoic acid, and 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 , C1 to C20 linear, branched, or tertiary amines such as ethylenediamine, morpholine, N-alkylmorpholine, cyclic amines such as pyridine, monoisopropanolamine, methylethanolamine, methylisopropanolamine, Examples include 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 in polyethylene glycol or polypropylene glycol that is end-capped with an alkyl group. If the repeating unit is small, the compatibility with the resin will be poor and the haze will increase, and if the repeating unit is large, the adhesiveness under high temperature and high humidity may be reduced. Nonionic, anionic, cationic, or amphoteric surfactants may be added to the blocked isocyanate of the present invention to improve water dispersibility.
  • nonionic systems such as polyethylene glycol and polyhydric alcohol fatty acid esters
  • anionic systems such as fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, sulfosuccinates, and alkyl phosphates
  • cationic systems such as alkylamine salts, and alkyl betaines
  • surfactants such as carboxylic acid amine salts, sulfonic acid amine salts, and sulfuric acid ester salts.
  • an antistatic agent is added to the composition constituting the functional adhesive layer.
  • the antistatic agent is preferably one that can suppress migration to other articles with which it comes in contact or to the back side of the film itself.
  • the functional group is nonionic such as sorbitan type, ether type, ester type, sorbitol type, glucose type, cationic type such as quaternary ammonium salt type, quaternary ammonium resin type, imidazoline type, arcobel type, solomine A type, etc.
  • alkyl sulfate type alkyl phosphate type, phosphate ester salt type, sulfate ester salt type, and other anionic surfactants, betaine type, amino acid type, amino sulfate ester type, and other amphoteric surfactant types or polymer types.
  • the counter ion of the quaternary ammonium base is not particularly limited as long as it is an anionic compound, but preferably a halogen ion, a mono- or polyhalogenated alkyl ion, a nitrate ion, or a sulfate ion. , alkyl sulfate ion, sulfonate ion, or alkyl sulfonate ion, but preferably the stability of surface resistivity value, stability of coating liquid, ink adhesion, and migration of antistatic agent to other articles or back surface. Ethosulfate salts are preferred in order to suppress this.
  • the urethane resin having a polycarbonate structure preferably contained in the composition constituting the functional adhesive layer preferably has a urethane bonding partial structure derived from at least a polycarbonate polyol component and a polyisocyanate component.
  • a chain extender may be included.
  • the polyisocyanate having a branched structure is synthesized and polymerized by the presence of three or more terminal functional groups of any of the above-mentioned raw materials constituting the molecular chain to form a branched molecular chain structure. It is preferable that it be suitably 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. . It is preferable that the number is 3 or more because blocking resistance when attached to water can be improved.
  • the upper limit of the number of terminal functional groups in the molecular chain 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 to polymerize the urethane resin having a polycarbonate structure in the present invention preferably contains an aliphatic polycarbonate polyol that has 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.
  • the aliphatic polycarbonate diol used for 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-pentane diol.
  • Diol one type of diol such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, etc.
  • examples include aliphatic polycarbonate diols obtained by reacting two or more types with carbonates such as dimethyl carbonate, ethylene carbonate, and phosgene.
  • the functional adhesive layer can also contain lubricant particles in order to impart slipperiness, matte properties, ink absorption properties, etc. to the surface.
  • Particles may be inorganic particles or organic particles, and are not particularly limited, but 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 / Organic particles such as butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, polyester, etc. are used, but in order to give the easy-adhesion layer appropriate slipperiness. Silica is particularly preferably used.
  • the average particle diameter of the particles is preferably 0.1 to 2.4 ⁇ m, more preferably 0.3 to 2.0 ⁇ m. If the average particle diameter of the particles is 0.1 ⁇ m or less, the glossiness of the film surface may increase. On the other hand, if the particle size exceeds 2.4 ⁇ m, the particles tend to fall off from the functional adhesion layer, causing powder falling.
  • the content of the particles can be added within a range that does not impede the effects of the present invention, but in order to prevent the particles from falling off the functional adhesive layer and causing powder falling, the content of the particles should be adjusted to a level that does not impede the effects of the present invention.
  • the solid content of the particles is preferably 0 to 70.0% by mass, preferably 0 to 60.0% by mass, and more preferably 0 to 55% by mass, based on the entire solid content of the functional adhesive layer. Preferably, it is .0% by mass.
  • the shape of the particles is not particularly limited as long as the object of the present invention is met, and spherical particles and irregularly shaped non-spherical particles can be used.
  • the particle diameter of irregularly shaped particles can be calculated as a circular equivalent diameter.
  • the polyester resin that can be preferably included in the composition forming the functional adhesive layer in the present invention may be a linear one, but more preferably a dicarboxylic acid and a diol having a branched structure. It is preferable that it is a polyester resin having as a constituent component.
  • the dicarboxylic acids mentioned here are 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, and dicarboxylic acids. , 6-naphthalene dicarboxylic acid and the like.
  • 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 preferably contained in a proportion of 10 mol% or more, more preferably 20 mol% or more, in the total glycol component. .
  • the upper limit of the glycol component in all glycol components is preferably 80 mol% or less, more preferably 70% by mass. When it is 80 mol% or less, the concentration of oligomers which are by-products is suppressed, and the transparency of the easily bonding layer is good, which is preferable.
  • Ethylene glycol is most preferred as a glycol component other than the above compounds. If the amount is small, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol, or the like may be used.
  • the dicarboxylic acid as a component of the polyester resin is most preferably terephthalic acid or isophthalic acid.
  • terephthalic acid or isophthalic acid in addition to the dicarboxylic acids mentioned above, in order to impart water dispersibility to the copolymerized polyester resin, it is preferable to copolymerize 5-sulfoisophthalic acid or the like in a range of 1 to 10 mol%, such as 5-sulfoisophthalic acid. Examples include dimethyl acid.
  • a polyester resin containing a dicarboxylic acid having a naphthalene skeleton may be used, but its quantitative proportion is 5 mol% or less in the total carboxylic acid component in order to suppress a decrease in adhesion to UV ink. is preferable, and may not be used.
  • triol or tricarboxylic acid may be included to the extent that the properties as a polyester resin are not impaired.
  • the above polyester resin may contain polar groups other than carboxyl groups.
  • sulfonic acid metal bases include sulfonic acid metal bases, phosphoric acid groups, etc., and one or more types of these can be used.
  • Methods for introducing the sulfonic acid metal base include metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-[4-sulfophenoxy]isophthalic acid, or 2-sulfo-1,
  • a dicarboxylic acid or glycol containing a sulfonic acid metal base such as a metal salt such as 4-butanediol, 2,5-dimethyl, 3-sulfo-2,5-hexanediol is used as a polycarboxylic acid component or a polyol component.
  • Examples include a method in which the amount is 10 mol % or less, preferably 7 mol % or less, and more preferably 5 mol % or less of the total amount. If it exceeds 10 mol%, the hydrolysis resistance of the resin itself and the water resistance of the coating film tend to decrease.
  • crosslinking agents include urea-based, epoxy-based, melamine-based, oxazoline-based, carbodiimide-based, and the like. Further, in order to promote the crosslinking reaction, a catalyst or the like can be appropriately used as necessary.
  • additives such as surfactants, pH adjusters, antioxidants, heat stabilizers, weather stabilizers, and ultraviolet absorbers may be added to the extent that they do not impede the effects of the present invention.
  • organic lubricants, pigments, dyes, organic or inorganic particles, nucleating agents, etc. may be added.
  • the coating step can be carried out by any method such as coating before stretching the film, coating after longitudinal stretching, or coating on the surface of the film after stretching.
  • a method for producing a hollow polyester easily adhesive film according to the present invention will be explained. For example, after drying a mixed pellet consisting of a composition containing a polyester resin, a polypropylene resin, and a silicone resin, it is melt-extruded into a sheet form from a T-shaped nozzle, and is brought into close contact with a casting drum using an electrostatic application method and cooled to solidify. , to obtain an unstretched film. Next, the unstretched film is stretched and oriented.
  • sequential biaxial stretching method particularly a method in which the unstretched film is longitudinally stretched in the longitudinal direction and then transversely stretched in the width direction, will be described. Let's explain with an example.
  • the film is heated and stretched by 2.5 to 5.0 times between two or multiple rolls having different circumferential speeds.
  • the heating means at this time may be a method using a heating roll or a method using a non-contact heating medium, or a combination of these methods may be used.
  • the temperature of the film is in the range of (Tg-10°C) to (Tg+50°C).
  • the uniaxially stretched film was applied by reverse gravure coating so that the wet coating amount was 1 to 20 g/m 2 , and then introduced into a tenter and coated in the width direction from (Tg - 10°C) to Tm - 10°C or less.
  • a biaxially stretched film can be obtained by stretching 2.5 to 5 times at a temperature of .
  • Tg is the glass transition temperature of the polyester resin
  • Tm is the melting point of the polyester.
  • the film obtained above is subjected to heat treatment if necessary, and the treatment temperature is preferably in the range of (Tm-60°C) to Tm.
  • the cavity-containing polyester-based easily adhesive film of the present invention can also contain, in the cavity-containing layer A, a recovered raw material made of the used cavity-containing polyester-based easily adhesive film of the present invention.
  • the used hollow-containing polyester-based easily adhesive film of the present invention is a scrap film generated from edges or breakage troubles that occurred during the film forming process, or one that is collected from the market. Even when adding recovered raw materials to the cavity-containing layer A, if the recovered raw materials of the cavity-containing polyester-based easily adhesive film of the present invention are used, the cavity development property can be maintained because a small amount of silicone resin is added to the polypropylene resin. .
  • the amount of the recovered raw material added is preferably 5 to 70% by mass based on 100% by mass of the total mass of the cavity-containing layer A, from the viewpoints of raw material cost reduction, whiteness, and film formability.
  • the first coating layer B1 or the second coating layer B2 may contain the recovered raw material, it is preferable not to contain it from the viewpoint of deterioration of whiteness and exposure of the polypropylene resin in the recovered raw material.
  • the apparent density of the cavity-containing polyester easily adhesive film in the present invention is preferably 0.80 g/cm 3 or more and 1.2 g/cm 3 or less, and preferably 0.80 g/cm 3 or more and 1.10 g/cm 3 or less. More preferred.
  • the apparent density is 0.80 g/cm3 or more and 1.20 g/ cm3 or less, the total amount of cavities in the void-containing polyester easy-adhesive film becomes an appropriate amount, making it difficult to handle during post-processing such as printing or during use. It becomes easier.
  • the apparent density is 0.80 g/cm 3 or more and 1.20 g/cm 3 or less, sufficient lightness and cushioning properties can be obtained.
  • the cavity-containing polyester-based easily adhesive film of the present invention contains a small amount of silicone resin, so it has excellent lightness, film formability, hiding property, and whiteness even when the apparent density is 0.80 to 1.10. has.
  • the apparent density is a value obtained by the measurement method described in the evaluation method described below.
  • the cavity-containing polyester easily adhesive film of the present invention preferably has a total light transmittance of 30% or less, more preferably 25% or less.
  • the total light transmittance is 30% or less, sufficient hiding performance can be obtained.
  • the images printed on the labels become clearer.
  • the total light transmittance is a value obtained in terms of a thickness of 50 ⁇ m obtained by the measurement method described in the evaluation method described below.
  • the cavity-containing polyester easily adhesive film of the present invention preferably has a color tone b value of 4.0 or less, more preferably 3.0 or less, particularly preferably 1.5 or less. If the color tone b value is greater than 4.0, the whiteness will be poor, and when printed on labels, etc., the clarity during printing may deteriorate, and the product value may be impaired.
  • the thickness of the cavity-containing polyester easily adhesive film of the present invention is arbitrary, it is preferably 20 ⁇ m or more and 300 ⁇ m or less.
  • the functional adhesive layer preferably has a residual area in close contact with the curable ink printed layer by the evaluation method described below of 90% or more of the total, and more preferably 99% or more.
  • the most preferable value is 100%.
  • the functional adhesive layer preferably contains an antistatic agent as described above, and preferably has a surface resistivity of 1.0 ⁇ 10 13 ⁇ /sq or less. More preferably, it is 1.0 ⁇ 10 12 ⁇ /sq or less, particularly preferably 1.0 ⁇ 10 11 ⁇ /sq or less. There is no particular lower limit, but it is preferably 1.0 ⁇ 10 5 ⁇ /sq or more, and preferably 1.0 ⁇ 10 6 ⁇ /sq or more.
  • the functional adhesive layer preferably has a pinhole-like repellency number of 5 pieces/m 2 or less according to the evaluation method described below. It is preferable that the number of pinhole-like repellents is as small as possible, and of course, the most preferable is 0 pieces/m 2 .
  • the functional adhesive layer of the cavity-containing polyester adhesive film of the present invention preferably has a water contact angle of 50 to 90° after heating at 150°C for 30 minutes. More preferably, the angle is between 55° and 85°. When this water contact angle is 90 degrees or less, the hollow polyester-based easily adhesive film can suppress coating omissions and printing omissions during processing steps.
  • This water contact angle is preferably small, but if a polyester resin is included, it is also preferably 50° or more. Further, it is preferable that the contact angle of diiodomethane after heating the functional adhesive layer at 150° C. for 30 minutes is 10 to 60°.
  • the cavity-containing polyester-based easily adhesive film can suppress coating omissions and printing omissions during processing steps.
  • the contact angle of diiodomethane is 10° or more, the cavity-containing polyester-based easily adhesive film can improve the adhesion between the coating and the original fabric in the processing process.
  • the functional adhesive layer of the hollow polyester adhesive film of the present invention preferably has a water contact angle of 46 to 90° after 72 hours at 85° C. and 85% RH. More preferably, the angle is 50° to 85°.
  • this water contact angle is 90 degrees or less, the hollow polyester-based easily adhesive film can suppress coating omission and printing omission when processed after long-term storage in a warehouse.
  • This water contact angle is preferably small, but if a polyester resin is included, it is also preferably 46° or more. Further, it is preferable that the contact angle of diiodomethane of the functional adhesive layer after 72 hours at 85° C. and 85% RH is 10 to 60°.
  • the void-containing polyester-based easily adhesive film can suppress coating omission and printing omission when processed after long-term storage in a warehouse.
  • the contact angle of diiodomethane is 10° or more, the cavity-containing polyester-based easily adhesive film can improve the adhesion between the coating and the original fabric in the processing process.
  • the cavity-containing polyester-based easy-adhesive film according to the present invention since the cavity-containing layer A contains a small amount of silicone resin, thermal deterioration of the polypropylene resin can be suppressed, for example, in the processing process, and cavity development can be maintained. Therefore, the cavity-containing polyester-based easily adhesive film according to the present invention has excellent lightness, film-forming properties, hiding properties, and whiteness even if the apparent density is 0.80 to 1.20.
  • the cavity-containing polyester easily adhesive film according to the present invention is suitably used as a base material for labels, cards, packaging materials, polarizing plates, release films used in the production of multilayer ceramic capacitors, and the like.
  • Color tone b value The color tone b value was measured according to JIS-8722 using a color difference meter (ZE6000) manufactured by Nippon Denshoku Co., Ltd. It is determined that the smaller the color tone b value, the higher the whiteness and the weaker the yellowish tinge.
  • the content of polydimethylsiloxane in the cavity-containing layer A was calculated using the layer ratio. Since the silicone resin is crosslinked and contains many insoluble components, it is difficult to quantify the amount added, but by using the above method, the soluble polydimethylsiloxane content in the silicone resin can be determined. It has been confirmed that there is a correlation between the amount of silicone resin added and the polydimethylsiloxane content.
  • Adhesion with UV ink UV ink [manufactured by T&K TOKA Co., Ltd., product name "BEST CURE (registered trademark) UV161 Indigo S”] is applied on the functional easy-adhesion layer of the hollow-containing polyester-based easy-adhesion film. Then, the film coated with the ink layer was irradiated with 40 mJ/cm 2 of ultraviolet rays using a high-pressure mercury lamp. The UV-curable ink was cured.
  • Example 1 Manufacture of titanium oxide master pellets (M1)] 50% by mass of anatase titanium dioxide having an average particle diameter of 0.3 ⁇ m (electron microscopy) was mixed with 50% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.62. The mixture was then supplied to a vented twin-screw extruder and kneaded to produce titanium oxide-containing master pellets (M1).
  • silicone resin S Thermosetting silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KS-774) was diluted with a solvent, and 3 parts by mass of a catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-3) was added to 100 parts by mass of the silicone resin, and 150 It was heated at °C for 60 seconds. After heating, the cured silicone resin was powdered to obtain silicone resin S.
  • a catalyst manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-3
  • [Functional adhesive layer] (Cationic antistatic agent A) An esterification reaction was carried out using 116 g of N,N-dimethyl-1,3-propanediamine and 285 g of stearic acid having 17 carbon atoms at 100°C in 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.
  • reaction solution was lowered to 50° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise.
  • the infrared spectrum of the reaction solution was measured to confirm that the absorption of isocyanate groups had disappeared, and 210 parts by mass of water was added to obtain an aqueous dispersion of oxime block isocyanate crosslinking agent (C) with a solid content of 40% by mass.
  • the number of functional groups of the blocked isocyanate crosslinking agent is 3, and the NCO equivalent is 170.
  • the temperature was raised to 255° C., the pressure of the reaction system was gradually reduced, and the reaction was carried out for 1 hour and 30 minutes under a reduced pressure of 30 Pa to obtain a copolymerized polyester resin (D-1).
  • the obtained copolymerized polyester resin (D-1) was pale yellow and transparent.
  • the reduced viscosity of the copolymerized polyester resin (D-1) was measured and found to be 0.40 dl/g.
  • the glass transition temperature by DSC was 65°C.
  • the solid content in the coating liquid of the coating compound constituting the functional adhesive layer is as follows.
  • the total solid content contained in the functional adhesive layer is 100% by mass.
  • ⁇ Cationic antistatic agent A 6.2% by mass
  • ⁇ Urethane resin B with polycarbonate structure 22.8% by mass
  • ⁇ Blocked isocyanate crosslinking agent C 10.9% by mass
  • ⁇ Polyester resin Dw-1 54.6% by mass
  • ⁇ Silicone surfactant 0.4% by mass ⁇ pH adjuster (sodium hydrogen carbonate): 2.4% by mass
  • the solid content mass ratio of urethane resin (B)/crosslinking agent (C)/polyester resin (Dw-1) is 28/12/60.
  • a cavity-containing polyester-based easily adhesive film was produced under the following film-forming conditions. That is, the obtained unstretched film was uniformly heated to 70° C. using a heating roll, and longitudinally stretched 3.4 times between two pairs of nip rolls having different circumferential speeds. At this time, as an auxiliary heating device for the unstretched film, an infrared heater (rated at 20 W/cm) equipped with a gold reflective film in the middle of the nip roll was installed facing both sides of the film (at a distance of 1 cm from the film surface), and heated. did.
  • Example 2 (Examples 2, 3, 5)
  • Example 1 a cavity-containing polyester-based easily adhesive film was obtained in the same manner as in Example 1, except that the raw material ratio of the cavity-containing layer A was changed as shown in Table 1.
  • Example 4 In Example 1, the cavity-containing polyester was prepared in the same manner as in Example 1, except that the raw material ratio and layer ratio of the cavity-containing layer A were changed as shown in Table 1, and the coating composition of the functional adhesive layer was changed as follows. An easily adhesive film was obtained.
  • the solid content in the coating liquid of the compound constituting the functional adhesive layer is as follows.
  • the total solid content contained in the functional adhesive layer is 100% by mass.
  • the structure of the functional easy-adhesive layer was the same as in Example 1 except that the wet coating amount was changed to 10 g/m 2 , except that the functional easy-adhesive layer had a thickness of 0.55 g/m 2 after drying.
  • a polyester containing easily adhesive film was obtained.
  • the gloss value of the surface of the functional adhesive layer in 60 degree specular reflection was 9.0%, and a functional adhesive layer with excellent matte feel was obtained.
  • Example 1 a cavity-containing polyester film was prepared in the same manner as in Example 1, except that the silicone resin in the cavity-containing layer A was changed to 0 ppm, the polyethylene terephthalate resin was changed to 93.08% by mass, and the functional adhesive layer was not provided. I got it.
  • the cavity-containing polyester film of Comparative Example 1 had an apparent density of more than 1.20 g/cm 3 and therefore had poor lightness and cushioning properties. Since the mass is large, the manufacturing cost is also high.
  • the cavity-containing polyester film of Comparative Example 1 has a high total light transmittance, has poor hiding properties compared to Examples 1 to 5, has poor UV ink adhesion due to the lack of a functional adhesive layer, and has no electrostatic charge. The film did not exhibit any preventive properties, and the films attracted each other due to static electricity, making it difficult to handle.
  • Example 2 In Example 1, a cavity-containing polyester-based easily adhesive film was obtained in the same manner as in Example 1, except that the layer ratio was changed to 0%. The total light transmittance was slightly high, and the hiding power was poor compared to Examples 1 to 5. In addition, the color tone b value was large, the whiteness was slightly lower than Examples 1 to 5, and the yellowish tinge was strong. In addition, in the cavity-containing polyester-based easy-adhesive film of Comparative Example 2, the appearance of the obtained functional easy-adhesive layer showed defects such as pinhole repellency due to the influence of the silicone resin. In addition, the UV ink applied to the functional adhesive layer also showed pinhole repellency and poor adhesion. . In Comparative Example 2, it is not possible to suppress coating omission in the processing step of the produced hollow-containing polyester-based easily adhesive film and printing omission in the next step.
  • Example 3 a cavity-containing polyester-based easily adhesive film was obtained in the same manner as in Example 1, except that the raw material ratio of the cavity-containing layer A was changed as shown in Table 1. Since the hollow polyester easily adhesive film of Comparative Example 3 had an apparent density lower than 0.80 g/cm 3 , the film itself had a weak feeling of stiffness and its surface strength was also reduced. The film forming properties of Comparative Example 3 were worse than those of Examples 1 to 5. As described above, in the cavity-containing polyester-based easily adhesive film according to the present invention, since the cavity-containing layer A contains a small amount of silicone resin, thermal deterioration of the polypropylene resin can be suppressed, for example, in the processing process, and cavity development can be maintained.
  • the cavity-containing polyester-based easy-adhesive film of the present invention has excellent easy-adhesive properties, and even with an apparent density of 0.80 to 1.20, it has excellent lightness, film-forming properties, hiding properties, and whiteness.
  • the cavity-containing polyester-based easy-adhesive films according to Examples 1 to 5 have excellent easy-adhesive properties, and even when the apparent density is 0.80 to 1.10, they have excellent lightness, film formability, concealment property, and white color. have a degree.
  • the cavity-containing polyester-based easy-adhesive film of the present invention has excellent lightness, film-forming properties, hiding properties, and whiteness, and has easy-adhesive properties, so it can be used, for example, in labels, cards, packaging materials, electronic materials, etc. It is suitably used as a base material for polarizing plates and release films used in the manufacture of multilayer ceramic capacitors.

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Abstract

This void-containing polyester-based easy adhesion film: has a first coating layer B1 that contains a polyester resin containing an inorganic pigment, a void-containing layer A that contains voids therein, and a second coating layer B2 that contains a polyester resin containing an inorganic pigment laminated in this order; has a functional easy adhesion layer on the first coating layer B1; and has an apparent density of 0.80 g/cm3 or greater and 1.20 g/cm3 or less, the void-containing layer A containing a composition that contains a polyester resin, a polypropylene resin, and a silicone resin.

Description

空洞含有ポリエステル系易接着フィルムHollow-containing polyester adhesive film
　本発明は、内部に空洞を含有する空洞含有ポリエステル系易接着フィルムに関するものである。 The present invention relates to a cavity-containing polyester-based easily adhesive film containing cavities inside.
　紙と類似した機能を有するフィルムを得る方法として、微細な空洞をフィルム内部に多量に含有させる方法が知られている。 A known method for obtaining a film with functions similar to paper is to include a large amount of fine cavities inside the film.
　この方法は、ポリエステル樹脂中に非相溶な熱可塑性樹脂（以下非相溶樹脂と呼ぶ）を混合し、ポリエステル樹脂中に該非相溶樹脂を分散させたシートを得て、少なくとも１軸方向に延伸する。これによりこの方法は、ポリエステル樹脂と非相溶樹脂との間での界面剥離によって、空洞を発現させる。このような非相溶樹脂として例えば、ポリエチレン樹脂やポリプロピレン樹脂、ポリメチルペンテン樹脂などのポリオレフィン樹脂（例えば、特許文献１～３参照）やポリスチレン樹脂（例えば、特許文献４、５参照）が提案されている。これらの中でポリプロピレン樹脂は、空洞発現性やコストパフォーマンスの点で優れている。 This method involves mixing an incompatible thermoplastic resin (hereinafter referred to as an incompatible resin) in a polyester resin to obtain a sheet in which the incompatible resin is dispersed in the polyester resin. Stretch. Accordingly, this method causes cavities to develop due to interfacial peeling between the polyester resin and the incompatible resin. As such incompatible resins, for example, polyolefin resins such as polyethylene resin, polypropylene resin, and polymethylpentene resin (see, for example, Patent Documents 1 to 3) and polystyrene resins (see, for example, Patent Documents 4 and 5) have been proposed. ing. Among these, polypropylene resin is excellent in terms of cavity development and cost performance.
　ここで、ポリプロピレン樹脂を単純にポリエステル樹脂に分散させた場合、ポリプロピレン分散粒子の分散径が大きくなる。そのため、空洞は発現し易いが、一方で空洞が大きくなってしまい、十分な隠蔽性が得られず、また製膜性も悪くなる。そのため、ポリプロピレン樹脂を微分散化させる方法が採用されてきた。これまで、この微分散化させる方法として、界面活性剤やポリエチレングリコールなどの分散剤を添加する方法が提案されている（例えば、特許文献６、７参照）。 Here, if the polypropylene resin is simply dispersed in the polyester resin, the dispersed diameter of the polypropylene dispersed particles becomes large. Therefore, cavities are likely to appear, but on the other hand, the cavities become large, making it impossible to obtain sufficient hiding properties and also deteriorating film forming properties. Therefore, a method of finely dispersing polypropylene resin has been adopted. Up to now, methods of adding a dispersant such as a surfactant or polyethylene glycol have been proposed as a method for achieving fine dispersion (see, for example, Patent Documents 6 and 7).
特開昭４９－１３４７５５号公報Japanese Unexamined Patent Publication No. 49-134755 特開平２－２８４９２９号公報Japanese Unexamined Patent Publication No. 2-284929 特開平２－１８０９３３号公報Japanese Unexamined Patent Publication No. 2-180933 特公昭５４－２９５５０号公報Special Publication No. 54-29550 特開平１１－１１６７１６号公報Japanese Patent Application Publication No. 11-116716 特公平７－１７７７９号公報Special Publication No. 7-17779 特開平８－２５２８５７号公報Japanese Patent Application Publication No. 8-252857
　しかしながら、界面活性剤やポリエチレングリコールなどの分散剤を添加した場合、ポリプロピレン樹脂に対して、微分散化効果はあるものの、加熱延伸工程や熱固定工程でポリプロピレン樹脂が変形してしまう。そのため、得られる空洞も潰れ易くなり、十分な軽量性やクッション性が得られない。また、界面活性剤やポリエチレングリコールは耐熱性に劣るため、ポリエステル樹脂に合わせた溶融押出工程において、熱劣化が生じ易く、得られるフィルムの白色度が低下してしまう。場合によっては、ポリエステル樹脂の劣化を促進し、製膜性が悪化する問題がある。 However, when a dispersant such as a surfactant or polyethylene glycol is added, although it has a fine dispersion effect on the polypropylene resin, the polypropylene resin is deformed during the heating stretching process and heat setting process. Therefore, the resulting cavity also tends to collapse, making it impossible to obtain sufficient lightness and cushioning properties. In addition, since surfactants and polyethylene glycol have poor heat resistance, they tend to undergo thermal deterioration during the melt extrusion process tailored to polyester resins, resulting in a decrease in the whiteness of the resulting film. In some cases, there is a problem that the deterioration of the polyester resin is accelerated and film forming properties are deteriorated.
　また、近年、印刷業界において、印刷の高速化が進んでおり、ＵＶ硬化型インキ等に対するより高い密着性が求められている。 Furthermore, in recent years, printing speeds have been increasing in the printing industry, and higher adhesion to UV-curable inks and the like is required.
　本発明の目的は、上記の従来技術の問題点を改善し、空洞発現剤としてポリプロピレン樹脂を主に使用した場合でも、軽量性、製膜性、隠蔽性、白色度、及び易接着性に優れた空洞含有ポリエステル系易接着フィルムを提供することである。 The purpose of the present invention is to improve the above-mentioned problems of the prior art, and to achieve excellent lightness, film-forming properties, hiding properties, whiteness, and easy adhesion even when polypropylene resin is mainly used as a cavity developing agent. An object of the present invention is to provide a hollow-containing polyester-based easily adhesive film.
　本発明者らは、鋭意検討を行った結果、極微量のシリコーン樹脂をポリプロピレン樹脂に添加することで、次のことを見出した。即ち本発明者らは、ポリエステル樹脂中のポリプロピレン分散粒子の耐熱性を向上させることができ、加熱延伸時や熱固定時におけるポリプロピレン分散粒子の変形を低減させることが可能となることを見出した。これにより本発明者らは、軽量性、製膜性、隠蔽性、及び白色度に優れた空洞含有ポリエステル系易接着フィルムが得られることを見出した。更に本発明者らは、積層構成とシリコーン樹脂添加量の調整により、シリコーン樹脂の副作用である塗工性、印刷性の悪化を抑制できる空洞含有ポリエステル系易接着フィルムを見出した。 As a result of extensive research, the present inventors discovered the following by adding a very small amount of silicone resin to polypropylene resin. That is, the present inventors have found that it is possible to improve the heat resistance of polypropylene dispersed particles in a polyester resin, and to reduce the deformation of the polypropylene dispersed particles during heat stretching and heat setting. As a result, the present inventors found that a hollow polyester-based easily adhesive film having excellent lightness, film-forming properties, concealing properties, and whiteness can be obtained. Furthermore, the present inventors have discovered a cavity-containing polyester-based easily adhesive film that can suppress deterioration in coatability and printability, which are side effects of silicone resins, by adjusting the laminated structure and the amount of silicone resin added.
　すなわち、本発明の空洞含有ポリエステル系易接着フィルムは、以下の構成よりなる。
１．　無機顔料を含有するポリエステル樹脂を含む第１被覆層Ｂ１と、内部に空洞を含有する空洞含有層Ａと、無機顔料を含有するポリエステル樹脂を含む第２被覆層Ｂ２と、がこの順序に積層され、前記第１被覆層Ｂ１上に機能性易接着層をし、
　見かけ密度が０．８０ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下であり、
　前記空洞含有層Ａが、ポリエステル樹脂とポリプロピレン樹脂とシリコーン樹脂を含有する組成物を含む空洞含有ポリエステル系易接着フィルム。
２．　前記空洞含有層Ａにおいて、シリコーン樹脂中のポリジメチルシロキサンの含有量が、空洞含有層Ａの全質量に対して１ｐｐｍ以上２５００ｐｐｍ以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
３．　前記空洞含有層Ａにおいて、シリコーン樹脂中のポリジメチルシロキサンの含有量が、ポリプロピレン樹脂１００質量％に対して０．００５質量％以上２．０００質量％以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
４．　前記第１被覆層Ｂ１及び前記第２被覆層Ｂ２中の無機顔料が酸化チタンである上記第１に記載の空洞含有ポリエステル系易接着フィルム。
５．　前記第１被覆層Ｂ１の厚み、前記空洞含有層Ａの厚み及び前記第２被覆層Ｂ２の厚みの合計に対する前記第１被覆層Ｂ１の厚み及び前記第２被覆層Ｂ２の厚みの合計の比率が、６％以上４０％以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
６．　全光線透過率が１％以上３０％以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
７．　見かけ密度が０．８０ｇ／ｃｍ３以上１．１０ｇ／ｃｍ３以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
８．　前記機能性易接着層の、以下の評価方法による密着残存面積が９９％以上である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
（但し、密着残存面積は、以下の評価方法による。
　空洞含有ポリエステル系易接着フィルムの機能性易接着層上に、ＵＶインキ［Ｔ＆Ｋ ＴＯＫＡ(株)製、商品名「ＢＥＳＴ ＣＵＲＥ（登録商標） ＵＶ１６１藍Ｓ」］を用いて、印刷機［(株)明製作所製、商品名「ＲＩテスター」］にて印刷を施し、次いで、インキ層を塗布したフィルムに高圧水銀灯を用いて４０ｍＪ／ｃｍ２の紫外線を照射し、紫外線硬化型インキを硬化させる。次いで、ニチバン製セロハン粘着テープ（CT405AP-24）を用い、幅２４ｍｍ、長さ５０ｍｍを切り出し、インキ層表面に空気が混入しないようハンディゴムローラーで完全に付着させる。その後、垂直にセロハン粘着テープを引き剥がして、２４ｍｍ×５０ｍｍの領域において、印刷層の残存した面積（密着残存面積）（％）を観察し求める。）
９．　前記機能性易接着層が帯電防止剤を含有しており、表面固有抵抗値が１．０×１０１３Ω／ｓｑ以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
１０．　前記機能性易接着層のピンホール状ハジキ個数が５個／ｍ２以下である上記第１に記載の空洞含有ポリエステル系易接着フィルム。
（但し、機能性易接着層のピンホール状ハジキ個数は、空洞含有ポリエステル系易接着フィルムの機能性易接着層を３波長蛍光灯下で目視観察によりピンホール状ハジキ個数を数えて評価する。）
１１．　ラベル、カード、包装材料、又は離型フィルムの用途に用いられる上記第１から上記第１０のいずれか１項に記載の空洞含有ポリエステル系易接着フィルム。 That is, the cavity-containing polyester easily adhesive film of the present invention has the following configuration.
1. A first coating layer B1 containing a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a second coating layer B2 containing a polyester resin containing an inorganic pigment are laminated in this order. , a functional adhesive layer is provided on the first coating layer B1,
The apparent density is 0.80 g/cm 3 or more and 1.20 g/cm 3 or less,
A cavity-containing polyester-based easily adhesive film in which the cavity-containing layer A includes a composition containing a polyester resin, a polypropylene resin, and a silicone resin.
2. The cavity-containing polyester easily adhesive film according to the above-mentioned item 1, wherein in the cavity-containing layer A, the content of polydimethylsiloxane in the silicone resin is 1 ppm or more and 2,500 ppm or less based on the total mass of the cavity-containing layer A.
3. In the cavity-containing layer A, the cavity-containing polyester according to the first aspect, wherein the content of polydimethylsiloxane in the silicone resin is 0.005% by mass or more and 2.000% by mass or less based on 100% by mass of the polypropylene resin. Easy adhesive film.
4. 1. The cavity-containing polyester-based easily adhesive film according to the above 1, wherein the inorganic pigment in the first coating layer B1 and the second coating layer B2 is titanium oxide.
5. The ratio of the sum of the thicknesses of the first coating layer B1 and the second coating layer B2 to the sum of the thickness of the first coating layer B1, the thickness of the cavity-containing layer A, and the thickness of the second coating layer B2 is , 6% or more and 40% or less, the void-containing polyester easily adhesive film according to the above-mentioned item 1.
6. The cavity-containing polyester easily adhesive film according to the above-mentioned item 1, which has a total light transmittance of 1% or more and 30% or less.
7. The cavity-containing polyester easily adhesive film according to the above item 1, which has an apparent density of 0.80 g/cm 3 or more and 1.10 g/cm 3 or less.
8. The cavity-containing polyester easy-adhesion film according to the above-mentioned item 1, wherein the functional easy-adhesion layer has a residual adhesion area of 99% or more according to the following evaluation method.
(However, the adhesion remaining area is based on the following evaluation method.
On the functional easy-adhesion layer of the hollow polyester-based easy-adhesion film, UV ink [manufactured by T&K TOKA Co., Ltd., product name "BEST CURE (registered trademark) UV161 Indigo S"] was applied to a printing machine [made by T&K TOKA Co., Ltd. Printing was carried out using a product named "RI Tester" manufactured by Mei Seisakusho, and then the film coated with the ink layer was irradiated with ultraviolet rays of 40 mJ/cm 2 using a high-pressure mercury lamp to cure the ultraviolet curable ink. Next, using Nichiban's cellophane adhesive tape (CT405AP-24), cut out a piece with a width of 24 mm and a length of 50 mm, and completely adhere it with a handy rubber roller to prevent air from entering the ink layer surface. Thereafter, the cellophane adhesive tape is peeled off vertically, and the remaining area of the printed layer (remaining adhesion area) (%) is observed and determined in an area of 24 mm x 50 mm. )
9. The cavity-containing polyester-based easy-adhesive film according to the above-mentioned item 1, wherein the functional easily-adhesive layer contains an antistatic agent and has a surface resistivity of 1.0×10 13 Ω/sq or less.
10. 1. The cavity-containing polyester-based easy-adhesion film according to the above-mentioned item 1, wherein the number of pinhole-like repellents in the functional easy-adhesion layer is 5 pieces/m 2 or less.
(However, the number of pinhole repellents in the functional adhesive layer is evaluated by visually observing the functional adhesive layer of the hollow polyester adhesive film under a three-wavelength fluorescent lamp and counting the number of pinhole repellents. )
11. The cavity-containing polyester easily adhesive film according to any one of the above items 1 to 10, which is used for labels, cards, packaging materials, or release films.
　本発明は、空洞発現剤としてポリプロピレン樹脂を主に含有する場合でも、軽量性、製膜性、隠蔽性、白色度、及び各種インキ等に対する密着性に優れた空洞含有ポリエステル系易接着フィルムを提供できる。 The present invention provides a cavity-containing polyester-based easily adhesive film that has excellent lightness, film-forming properties, hiding properties, whiteness, and adhesion to various inks even when it mainly contains polypropylene resin as a cavity developer. can.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be explained in detail.
　本発明の空洞含有ポリエステル系易接着フィルムは、無機顔料を含有するポリエステル樹脂からなる第１被覆層Ｂ１と、内部に空洞を含有する空洞含有層Ａと、無機顔料を含有するポリエステル樹脂からなる第２被覆層Ｂ２と、がこの順序に積層された積層体であることが好ましい。この空洞含有層Ａは、ポリエステル樹脂とポリプロピレン樹脂とシリコーン樹脂を含有する組成物からなることが好ましい。また、この空洞含有ポリエステル系易接着フィルムの見かけ密度は０．８０ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下であることが好ましい。 The cavity-containing polyester-based easily adhesive film of the present invention comprises a first coating layer B1 made of a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a first coating layer B1 made of a polyester resin containing an inorganic pigment. It is preferable that the two coating layers B2 and B2 are laminated in this order. This cavity-containing layer A is preferably made of a composition containing a polyester resin, a polypropylene resin, and a silicone resin. Further, the apparent density of this hollow-containing polyester-based easily adhesive film is preferably 0.80 g/cm 3 or more and 1.20 g/cm 3 or less.
　空洞含有層Ａ、第１被覆層Ｂ１及び第２被覆層Ｂ２の主成分となるポリエステル樹脂は、ジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成性誘導体から合成されるポリマーであることが好ましい。このようなポリエステル樹脂の代表例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン－２，６－ナフタレートが挙げられる。これらのうち、機械的特性および耐熱性、コストなどの観点からポリエチレンテレフタレートが好ましい。 The polyester resin that is the main component of the cavity-containing layer A, the first coating layer B1, and the second coating layer B2 is a polymer synthesized from dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative. is preferred. Typical examples of such polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate. Among these, polyethylene terephthalate is preferred from the viewpoint of mechanical properties, heat resistance, cost, and the like.
　また、これらのポリエステル樹脂には、本発明の目的が損なわれない範囲であれば、他の成分が共重合されていてもよい。具体的には、共重合成分としては、ジカルボン酸成分では、イソフタル酸、ナフタレンジカルボン酸、４、４－ジフェニルジカルボン酸、アジピン酸、セバシン酸およびそのエステル形成性誘導体などが挙げられる。また、ジオール成分としてはジエチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノールが挙げられる。また、ポリエチレングリコール、ポリプロピレングリコール等のポリオキシアルキレングリコールも挙げられる。共重合量としては、構成する繰り返し単位あたり１０モル％以内が好ましく、５モル％以内がより好ましい。 Further, other components may be copolymerized with these polyester resins as long as the purpose of the present invention is not impaired. Specifically, the copolymerization component includes dicarboxylic acid components such as isophthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid, and ester-forming derivatives thereof. Further, diol components include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol. Also included are polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol. The amount of copolymerization is preferably within 10 mol%, more preferably within 5 mol%, per repeating unit.
　ポリエステル樹脂の製造方法としては例えば、まず、前述のジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成誘導体とを主たる出発原料とすることが好ましい。次に常法に従い、エステル化またはエステル交換反応を行った後、さらに高温・減圧下で重縮合反応を行うことによって製造することが好ましい。 As a method for producing a polyester resin, for example, it is preferable to first use the above-mentioned dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative as the main starting materials. Next, it is preferable to carry out an esterification or transesterification reaction according to a conventional method, followed by a polycondensation reaction at high temperature and reduced pressure.
　ポリエステル樹脂の極限粘度は、製膜性や回収利用性などの点から０．５０ｄｌ／ｇ以上０．９ｄｌ／ｇ以下が好ましく、より好ましくは０．５５ｄｌ／ｇ以上０．８５ｄｌ／ｇ以下である。 The intrinsic viscosity of the polyester resin is preferably 0.50 dl/g or more and 0.9 dl/g or less, more preferably 0.55 dl/g or more and 0.85 dl/g or less, from the viewpoint of film formability, recovery and utilization, etc. .
　ポリエステル樹脂の含有量は、空洞含有層Ａ中に含まれる全成分の合計１００質量％に対して、７０質量％以上９７質量％以下が好ましく、７５質量％以上９５質量％以下が更に好ましい。ポリエステル樹脂の含有量が７０質量％以上である場合、空洞含有ポリエステル系易接着フィルムは、製膜性の悪化を抑制することができる。ポリエステル樹脂の含有量が９７％以下である場合、空洞含有ポリエステル系易接着フィルムは、ポリプロピレン樹脂及びシリコーン樹脂の添加により、空洞を形成させることができる。 The content of the polyester resin is preferably 70% by mass or more and 97% by mass or less, and more preferably 75% by mass or more and 95% by mass or less, based on a total of 100% by mass of all components contained in the cavity-containing layer A. When the content of the polyester resin is 70% by mass or more, the cavity-containing polyester-based easily adhesive film can suppress deterioration in film formability. When the content of polyester resin is 97% or less, cavities can be formed in the cavity-containing polyester-based easily adhesive film by adding polypropylene resin and silicone resin.
　次に、本発明で空洞発現剤として使用される非相溶樹脂であるポリプロピレン樹脂について説明する。本発明の空洞含有ポリエステル系易接着フィルムは、特定の層構成を採用し、特定のポリプロピレン樹脂を用いることで空洞発現性を維持できる。これにより、本発明の空洞含有ポリエステル系易接着フィルムは、十分な軽量性やクッション性が得られるとともに、製膜性、隠蔽性。及び白色度に優れる。 Next, polypropylene resin, which is an incompatible resin used as a cavity developing agent in the present invention, will be explained. The cavity-containing polyester-based easily adhesive film of the present invention can maintain cavity development by adopting a specific layer structure and using a specific polypropylene resin. As a result, the cavity-containing polyester easily adhesive film of the present invention has sufficient lightness and cushioning properties, as well as excellent film formability and concealment properties. and excellent whiteness.
　本発明で使用するポリプロピレン樹脂は、好ましくは９５モル％以上、より好ましくは９８モル％以上のプロピレン単位を有する結晶性ポリプロピレンが好ましい。特に好ましくは、プロピレン単位が１００モル％の結晶性ポリプロピレンホモポリマーである。 The polypropylene resin used in the present invention is preferably a crystalline polypropylene having propylene units of 95 mol% or more, more preferably 98 mol% or more. Particularly preferred is a crystalline polypropylene homopolymer containing 100 mol% of propylene units.
　本発明で使用するポリプロピレン樹脂は、空洞発現性や製膜性の観点から、メルトフローレート（ＭＦＲ）が１．０ｇ／１０分以上１０．０ｇ／１０分以下が好ましく、１．５ｇ／１０分以上７．０ｇ／分以下が更に好ましい。ＭＦＲが１．０ｇ／１０分以上１０．０ｇ／１０分以下である場合、ダイスから押し出されるときにポリプロピレン分散粒子が変形し難くなるため、空洞を形成し易くなる。さらに、ＭＦＲが１．０ｇ／１０分以上１０．０ｇ／１０分以下である場合、ポリプロピレン分散粒子の分散性も優れ、十分な隠蔽性が得られ、製膜性も優れる。尚、メルトフローレート（ＭＦＲ）は、ＪＩＳ　Ｋ　７２１０に準じ、２３０℃、荷重２．１６ｋｇの条件下での測定値である。 The polypropylene resin used in the present invention preferably has a melt flow rate (MFR) of 1.0 g/10 minutes to 10.0 g/10 minutes, and 1.5 g/10 minutes from the viewpoint of cavity development and film forming properties. It is more preferably 7.0 g/min or less. If the MFR is 1.0 g/10 minutes or more and 10.0 g/10 minutes or less, the polypropylene dispersed particles will be difficult to deform when extruded from the die, making it easier to form cavities. Furthermore, when the MFR is 1.0 g/10 minutes or more and 10.0 g/10 minutes or less, the dispersibility of the polypropylene dispersed particles is excellent, sufficient hiding properties are obtained, and film forming properties are also excellent. Note that the melt flow rate (MFR) is a value measured under the conditions of 230° C. and a load of 2.16 kg according to JIS K 7210.
　本発明で使用するポリプロピレン樹脂では、空洞発現性の観点から、荷重たわみ温度が８５℃以上であることが好ましく、９０℃以上であることがより好ましく、９５℃以上であることが更に好ましい。上限としては、特に制限する必要はないが、１３５℃以下が好ましい。荷重たわみ温度が８５℃以上である場合、特に、後述するポリエステル樹脂のガラス転移温度以上で加熱してフィルムを延伸する縦延伸工程において、ポリプロピレン分散粒子が潰れ難くなるため、空洞が形成し易くなる。尚、荷重たわみ温度は、ＪＩＳ　Ｋ　７１９１－１、２のＢ法に準じ、試験片の曲げ応力が０．４５ＭＰａのときの測定値である。 In the polypropylene resin used in the present invention, from the viewpoint of cavity development, the deflection temperature under load is preferably 85°C or higher, more preferably 90°C or higher, and even more preferably 95°C or higher. The upper limit is not particularly limited, but is preferably 135°C or lower. When the deflection temperature under load is 85° C. or higher, the polypropylene dispersed particles become difficult to collapse, making it easier to form cavities, especially in the longitudinal stretching process in which the film is stretched by heating at a temperature higher than the glass transition temperature of the polyester resin, which will be described later. . Note that the deflection temperature under load is a value measured when the bending stress of the test piece is 0.45 MPa according to method B of JIS K 7191-1, 2.
　本発明で使用するポリプロピレン樹脂は、空洞発現性や押出工程および回収工程での熱劣化を抑える観点から、重量平均分子量（Ｍｗ）は２０００００以上４５００００以下が好ましく、２５００００以上４０００００以下がより好ましい。Ｍｗが４５００００以下である場合、ポリプロピレン分散粒子の分散性が良くなり、十分な隠蔽性が得られ、製膜性に優れる。Ｍｗが２０００００以上である場合、ポリプロピレン分散粒子が変形し難くなるため、空洞を形成し易くなる。Ｍｗが２０００００以上である場合、回収原料を使用した場合でも、空洞発現性が低下することを抑制できるため、好ましい。 The weight average molecular weight (Mw) of the polypropylene resin used in the present invention is preferably 200,000 or more and 450,000 or less, more preferably 250,000 or more and 400,000 or less, from the viewpoint of cavity development and suppressing thermal deterioration in the extrusion process and recovery process. When Mw is 450,000 or less, the dispersibility of the polypropylene dispersed particles is improved, sufficient hiding properties are obtained, and film forming properties are excellent. When Mw is 200,000 or more, the polypropylene dispersed particles become difficult to deform, making it easier to form cavities. When Mw is 200,000 or more, it is preferable because it is possible to suppress a decrease in cavity development even when recovered raw materials are used.
　また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比である分子量分布（Ｍｗ／Ｍｎ）は、２以上６以下が好ましく、２以上５以下がより好ましい。Ｍｗ／Ｍｎは、分子量分布の広がりを表す指標であり、この値が大きいほど、分子量分布が広いことを意味する。Ｍｗ／Ｍｎが６以下である場合、低分子量成分が減るため、回収原料を使用した場合でも、白色度及び空洞発現性の低下を抑制でき、好ましい。また、Ｍｗ／Ｍｎが２以上であればコスト上の観点から工業生産に適している。尚、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した値である。 Furthermore, the molecular weight distribution (Mw/Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), is preferably 2 or more and 6 or less, and more preferably 2 or more and 5 or less. Mw/Mn is an index representing the spread of molecular weight distribution, and the larger this value is, the wider the molecular weight distribution is. When Mw/Mn is 6 or less, low molecular weight components are reduced, so even when recycled raw materials are used, reduction in whiteness and cavity development can be suppressed, which is preferable. Moreover, if Mw/Mn is 2 or more, it is suitable for industrial production from a cost standpoint. Note that the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC).
　ポリプロピレン樹脂の含有量は、空洞発現性や製膜性の観点から、空洞含有層Ａ中に含まれる全成分の合計１００質量％に対して、３質量％以上３０質量％以下が好ましく、５質量％以上２５質量％以下が更に好ましい。ポリプロピレン樹脂の含有量が３質量％以上３０質量％以下である場合、十分な軽量性やクッション性を得るための空洞を形成させることができるとともに、製膜性に優れる。 From the viewpoint of cavity development and film forming properties, the content of the polypropylene resin is preferably 3% by mass or more and 30% by mass or less, and 5% by mass or less, based on the total 100% by mass of all components contained in the cavity-containing layer A. % or more and 25% by mass or less is more preferable. When the content of the polypropylene resin is 3% by mass or more and 30% by mass or less, cavities can be formed to obtain sufficient lightness and cushioning properties, and the film-forming properties are excellent.
　本発明に使用されるシリコーン樹脂としては、シリコーンポリマー、例えば、一部架橋型のシリコーンポリマー（即ち、狭義のシリコーン樹脂であるシリコーンレジン）及び直鎖状のシリコーンポリマー（即ち、シリコーンゴム）が挙げられる。具体的にはメチルシリコーン樹脂、メチルフェニルシリコーン樹脂、フェニルシリコーン樹脂、アルキッド変性シリコーン樹脂、ポリエステル変性シリコーン樹脂、ウレタン変性シリコーン樹脂、エポキス変性シリコーン樹脂、アクリル変性シリコーン樹脂が挙げられる。ベース樹脂であるポリエステル樹脂の押出温度に耐えられる点、昇華による工程汚染を抑制する観点から架橋構造をもつシリコーン樹脂が好ましい。 Examples of the silicone resin used in the present invention include silicone polymers, such as partially crosslinked silicone polymers (i.e., silicone resins that are silicone resins in the narrow sense) and linear silicone polymers (i.e., silicone rubber). It will be done. Specific examples include methyl silicone resin, methylphenyl silicone resin, phenyl silicone resin, alkyd-modified silicone resin, polyester-modified silicone resin, urethane-modified silicone resin, epoxy-modified silicone resin, and acrylic-modified silicone resin. A silicone resin having a crosslinked structure is preferred from the viewpoint of being able to withstand the extrusion temperature of the polyester resin that is the base resin and suppressing process contamination due to sublimation.
　シリコーン樹脂を添加する方法としては、特に限定されないが、パウダー状、ペレット状のものをベース樹脂とドライブレンドして添加する直接添加でも良い。事前にポリエステル樹脂、ポリプロピレン樹脂、シリコーン樹脂を溶融混合したマスターバッチを作製しても良い。 The method of adding the silicone resin is not particularly limited, but it may be directly added by dry blending a powder or pellet with the base resin. A masterbatch may be prepared in advance by melt-mixing polyester resin, polypropylene resin, and silicone resin.
　シリコーン樹脂の添加量は空洞発現性や製膜性や製造コストの観点から、空洞含有層Ａの全質量に対して、１ｐｐｍ以上１００００ｐｐｍ以下が好ましく、１００ｐｐｍ以上８０００ｐｐｍ以下が更に好ましい。１ｐｐｍ以上にすることで見かけ密度を効率的に下げることができる。１００００ｐｐｍ以下にすることで工程汚染や製膜性の悪化を抑制することができる。さらには製造コストを抑えることができる。 The amount of silicone resin added is preferably 1 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 8,000 ppm or less, based on the total mass of the cavity-containing layer A, from the viewpoint of cavity development, film formability, and manufacturing cost. By setting the content to 1 ppm or more, the apparent density can be efficiently lowered. By controlling the content to 10,000 ppm or less, it is possible to suppress process contamination and deterioration of film formability. Furthermore, manufacturing costs can be reduced.
　シリコーン樹脂由来のポリジメチルシロキサンの含有量は、ＮＭＲ（核磁気共鳴）法から求められる。シリコーン樹脂由来のポリジメチルシロキサンの含有量は、空洞発現性や製膜性や製造コストの観点から、空洞含有層Ａの全質量に対して、１ｐｐｍ以上２５００ｐｐｍ以下が好ましく、１００ｐｐｍ以上２４００ｐｐｍ以下が更に好ましい。１００ｐｐｍ以上１４００ｐｐｍ以下が更により好ましい。１ｐｐｍ以上にすることで見かけ密度を効率的に下げることができる。２５００ｐｐｍ以下にすることで工程汚染や製膜性の悪化を抑制することができる。さらには製造コストを抑えることができる。シリコーン樹脂は架橋構造を有しており、溶媒に不溶であることから後述するＮＭＲ測定方法を用いて、シリコーン樹脂内に存在するポリジメチルシロキサンの含有量を求めることで空洞含有層Ａ中のシリコーン樹脂の含有量の指標とすることができる。 The content of polydimethylsiloxane derived from silicone resin is determined by NMR (nuclear magnetic resonance) method. The content of polydimethylsiloxane derived from silicone resin is preferably 1 ppm or more and 2,500 ppm or less, more preferably 100 ppm or more and 2,400 ppm or less, based on the total mass of the cavity-containing layer A, from the viewpoint of cavity development, film formability, and manufacturing cost. preferable. Even more preferably 100 ppm or more and 1400 ppm or less. By setting the content to 1 ppm or more, the apparent density can be efficiently lowered. By controlling the content to 2500 ppm or less, it is possible to suppress process contamination and deterioration of film formability. Furthermore, manufacturing costs can be reduced. Since silicone resin has a crosslinked structure and is insoluble in solvents, the content of polydimethylsiloxane present in the silicone resin can be determined using the NMR measurement method described later. It can be used as an index of resin content.
　ＮＭＲ法から求められる空洞含有層Ａに含まれるシリコーン樹脂中のポリジメチルシロキサンの含有量は、空洞含有層Ａ中のポリプロピレン樹脂１００質量％に対して０．００５質量％以上２．０００質量％以下であることが好ましい。０．０１０質量％以上１．８００質量％以下が更に好ましい。０．１００質量％以上０．８００質量％以下が更により好ましい。ポリプロピレン樹脂１００質量％に対して、０．００５質量％以上含有することでポリプロピレン樹脂の耐熱性が向上し、延伸時につぶれることなく空洞を効率的に発現させることができる。２．０００質量％以下にすることで、製膜性の悪化を抑制することができる。 The content of polydimethylsiloxane in the silicone resin contained in the cavity-containing layer A determined by the NMR method is 0.005% by mass or more and 2.000% by mass or less based on 100% by mass of the polypropylene resin in the cavity-containing layer A. It is preferable that More preferably 0.010% by mass or more and 1.800% by mass or less. Even more preferably 0.100% by mass or more and 0.800% by mass or less. By containing 0.005% by mass or more based on 100% by mass of the polypropylene resin, the heat resistance of the polypropylene resin is improved, and cavities can be efficiently developed without being crushed during stretching. By setting the content to 2.000% by mass or less, deterioration in film formability can be suppressed.
　空洞含有層Ａがシリコーン樹脂を微量に含有することで、ポリプロピレン樹脂に耐熱性を付与することができる。そのため、マテリアルリサイクルする際にポリプロピレン樹脂の熱劣化を抑制でき、空洞発現性を維持できる効果がある。空洞含有ポリエステル系易接着フィルムとしても、高温環境下で空洞が潰れにくくなるため、局所的にボイド発現剤であるポリプロピレン樹脂がつぶれることによる厚みムラを抑制することができる。 By containing a trace amount of silicone resin in the cavity-containing layer A, heat resistance can be imparted to the polypropylene resin. Therefore, it is possible to suppress thermal deterioration of the polypropylene resin during material recycling, and it has the effect of maintaining cavity development. Even in the case of a cavity-containing polyester-based easily adhesive film, the cavities are less likely to collapse in a high-temperature environment, so it is possible to suppress thickness unevenness caused by local collapse of the polypropylene resin, which is a void generator.
　また、本発明の目的を損なわない範囲であれば、ポリプロピレン樹脂以外の非相溶樹脂が含有されていてもよい。空洞含有層Ａ中の非相溶樹脂合計１００質量％に対して、ポリプロピレン樹脂が９０質量％以上含有していることが好ましく、９５質量％以上が更に好ましく、最も好ましくは１００質量％である。また、白色度や空洞発現性の観点からポリエチレングリコールや界面活性剤等の分散剤を含まないことが好ましい。 Furthermore, incompatible resins other than polypropylene resin may be contained within a range that does not impair the purpose of the present invention. The content of the polypropylene resin is preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass, based on the total 100% by mass of the incompatible resins in the cavity-containing layer A. Further, from the viewpoint of whiteness and cavity development, it is preferable not to contain a dispersant such as polyethylene glycol or a surfactant.
　また、本発明の目的を損なわない範囲において、これらのポリエステル樹脂またはポリプロピレン樹脂中には、少量の他の重合体や酸化防止剤、熱安定剤、艶消し剤、顔料、紫外線吸収剤、蛍光増白剤、可塑剤又はその他の添加剤などが含有されていてもよい。特に、ポリプロピレン樹脂の酸化劣化を抑えるために、酸化防止剤もしくは熱安定剤を含有させることが好ましい。酸化防止剤および熱安定剤の種類としては、特に限定されないが、例えば、ヒンダートフェノール系、リン系、ヒンダードアミン系などが挙げられ、これらは単体でも併用して使用してもよい。添加量としては、空洞含有層Ａの全質量に対して１ｐｐｍ以上５００００ｐｐｍ以下が好ましい。なお、本発明では、蛍光増白剤を空洞含有層Ａ中に添加しなくても、優れた白色度を確保することができる。 In addition, to the extent that the purpose of the present invention is not impaired, these polyester resins or polypropylene resins may contain small amounts of other polymers, antioxidants, heat stabilizers, matting agents, pigments, ultraviolet absorbers, and fluorescent enhancers. A whitening agent, a plasticizer, or other additives may also be contained. In particular, in order to suppress oxidative deterioration of the polypropylene resin, it is preferable to include an antioxidant or a heat stabilizer. The types of antioxidants and heat stabilizers are not particularly limited, but include, for example, hindered phenol type, phosphorus type, hindered amine type, etc., and these may be used alone or in combination. The amount added is preferably 1 ppm or more and 50,000 ppm or less based on the total mass of the cavity-containing layer A. In addition, in the present invention, excellent whiteness can be ensured even without adding a fluorescent brightener to the cavity-containing layer A.
　本発明において、空洞含有ポリエステル系易接着フィルムには、隠蔽性や白色度を向上させるため、ポリエステル樹脂中またはポリプロピレン樹脂中に、無機顔料を必要に応じて含有させることができる。無機顔料としては、シリカ、カオリナイト、タルク、炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、酸化チタン、硫化亜鉛等が挙げられる。これらのうち、隠蔽性や白色度の観点から、酸化チタン、炭酸カルシウム、硫酸バリウムが好ましい。また、これらの無機顔料は、単体で用いても、もしくは二種類以上併用してもよい。これらの無機顔料は、予めポリエステル樹脂中もしくはポリプロピレン樹脂中に添加することにより、空洞含有ポリエステル系易接着フィルム内に含有させることができる。 In the present invention, an inorganic pigment can be contained in the polyester resin or polypropylene resin as necessary in the hollow polyester-based easy-adhesive film in order to improve hiding properties and whiteness. Examples of inorganic pigments include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, titanium oxide, and zinc sulfide. Among these, titanium oxide, calcium carbonate, and barium sulfate are preferred from the viewpoint of hiding power and whiteness. Further, these inorganic pigments may be used alone or in combination of two or more. These inorganic pigments can be incorporated into the cavity-containing polyester-based easily adhesive film by adding them to the polyester resin or polypropylene resin in advance.
　ポリエステル樹脂またはポリプロピレン樹脂に、無機顔料を混合する方法としては、特に限定されないが、次の方法が挙げられる。すなわち、ポリエステル樹脂とポリプロピレン樹脂をドライブレンド後、そのまま製膜機に投入する方法、ポリエステル樹脂とポリプロピレン樹脂をドライブレンド後、種々の一般的な混練機を用いて溶融混練しマスターバッチ化する方法などが挙げられる。 The method of mixing the inorganic pigment with the polyester resin or polypropylene resin is not particularly limited, but the following method may be mentioned. Namely, there are methods such as dry blending polyester resin and polypropylene resin and then feeding them directly into a film forming machine, dry blending polyester resin and polypropylene resin, and then melt-kneading them using various general kneading machines to form a masterbatch. can be mentioned.
　本発明の空洞含有ポリエステル系易接着フィルムは、無機顔料を含有するポリエステル樹脂からなる第１被覆層Ｂ１と、内部に空洞を含有する空洞含有層Ａと、無機顔料を含有するポリエステル樹脂からなる第２被覆層Ｂ２と、がこの順序に積層された積層構造を有する。ここで、ポリプロピレン樹脂を含む空洞含有層Ａが表層に露出した場合、一部の露出したポリプロピレン分散粒子が、ロール汚れなどの工程汚染を発生させてしまう。また、無機顔料を含んだ第１被覆層Ｂ１及び第２被覆層Ｂ２が、空洞含有層Ａを被覆することで、白色度の低下を防ぐ効果を有する。 The cavity-containing polyester-based easily adhesive film of the present invention comprises a first coating layer B1 made of a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a first coating layer B1 made of a polyester resin containing an inorganic pigment. It has a laminated structure in which two coating layers B2 are laminated in this order. Here, if the cavity-containing layer A containing the polypropylene resin is exposed to the surface layer, some of the exposed polypropylene dispersed particles will cause process contamination such as roll stains. Moreover, the first coating layer B1 and the second coating layer B2 containing an inorganic pigment cover the cavity-containing layer A, thereby having the effect of preventing a decrease in whiteness.
　第１被覆層Ｂ１の厚み、空洞含有層Ａの厚み及び第２被覆層Ｂ２の厚みの合計に対する第１被覆層Ｂ１の厚み及び第２被覆層Ｂ２の厚みの合計の比率（以下、層比率と称することもある。）は、空洞発現性やポリプロピレン樹脂とシリコーン樹脂の露出抑制の観点から、６％以上４０％以下が好ましく、８％以上３０％以下であることがより好ましい。層比率が６％以上４０％以下である場合、ポリプロピレン樹脂とシリコーン樹脂の露出を抑制でき、水の接触角及びジヨードメタンの接触角を低くできる。さらに、層比率が６％以上４０％以下である場合、十分な軽量性やクッション性を得るための空洞を形成させることが容易である。 The ratio of the total thickness of the first coating layer B1 and the second coating layer B2 to the sum of the thickness of the first coating layer B1, the thickness of the cavity-containing layer A, and the thickness of the second coating layer B2 (hereinafter referred to as layer ratio) ) is preferably 6% or more and 40% or less, more preferably 8% or more and 30% or less, from the viewpoint of cavity development and suppression of exposure of the polypropylene resin and silicone resin. When the layer ratio is 6% or more and 40% or less, exposure of the polypropylene resin and silicone resin can be suppressed, and the contact angle of water and the contact angle of diiodomethane can be reduced. Furthermore, when the layer ratio is 6% or more and 40% or less, it is easy to form cavities for obtaining sufficient light weight and cushioning properties.
　第１被覆層Ｂ１及び第２被覆層Ｂ２に含有する無機顔料としては、シリカ、カオリナイト、タルク、炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、酸化チタン、硫化亜鉛等が挙げられる。これらのうち、隠蔽性や白色度の観点から、酸化チタン、炭酸カルシウム、硫酸バリウムが好ましく、酸化チタンが特に好ましい。また、これらの無機顔料は、単体で用いても、もしくは二種類以上併用してもよい。これらの顔料は、予めポリエステル樹脂中に添加することにより、フィルム内に含有させることができる。 Examples of the inorganic pigments contained in the first coating layer B1 and the second coating layer B2 include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, titanium oxide, zinc sulfide, and the like. Among these, titanium oxide, calcium carbonate, and barium sulfate are preferred from the viewpoint of hiding power and whiteness, and titanium oxide is particularly preferred. Further, these inorganic pigments may be used alone or in combination of two or more. These pigments can be incorporated into the film by adding them to the polyester resin in advance.
　第１被覆層Ｂ１中の無機顔料の添加量は、特に限定されないが、第１被覆層Ｂ１を構成する全成分１００質量％に対して、１質量％以上３５質量％以下が好ましく、より好ましくは２質量％以上３０質量％以下である。無機顔料の添加量が１質量％以上３５質量％以下である場合、空洞含有ポリエステル系易接着フィルムの隠蔽性や白色度を向上させることが容易であるとともに、空洞含有ポリエステル系易接着フィルムの製膜性や機械的強度を向上させることができる。 The amount of the inorganic pigment added in the first coating layer B1 is not particularly limited, but is preferably 1% by mass or more and 35% by mass or less, more preferably It is 2% by mass or more and 30% by mass or less. When the amount of the inorganic pigment added is 1% by mass or more and 35% by mass or less, it is easy to improve the hiding property and whiteness of the hollow polyester adhesive film, and the production of the hollow polyester adhesive film is easy. Film properties and mechanical strength can be improved.
　第２被覆層Ｂ２中の無機顔料の添加量は、特に限定されないが、第１被覆層Ｂ１中の無機顔料の添加量と同じであることが好ましい。第１被覆層Ｂ１と第２被覆層Ｂ２は実質的にその組成や厚みなどにおいて同一であることも好ましい。即ち、第１被覆層Ｂ１／空洞含有層Ａ／第２被覆層Ｂ２の積層構成は２種３層構成であることも好ましい。そして、第１被覆層Ｂ１上に機能性易接着層が積層されていることが好ましいが、第２被覆層Ｂ２に、第１被覆層Ｂ１上の機能性易接着層と同一又は組成や厚みなどが異なる機能性易接着層が積層されていることも好ましい。 The amount of the inorganic pigment added in the second coating layer B2 is not particularly limited, but it is preferably the same as the amount of the inorganic pigment added in the first coating layer B1. It is also preferable that the first coating layer B1 and the second coating layer B2 are substantially the same in composition, thickness, and the like. That is, it is also preferable that the laminated structure of the first coating layer B1/cavity-containing layer A/second coating layer B2 is a two-type, three-layer structure. It is preferable that a functional adhesive layer is laminated on the first coating layer B1, and the second coating layer B2 has the same composition or thickness as the functional adhesive layer on the first coating layer B1. It is also preferable that functional adhesion layers having different values are laminated.
　第１被覆層Ｂ１及び第２被覆層Ｂ２に含有される無機顔料は粒子状のものであることが好ましく、粒子の平均粒子径が０．１～４．０μｍであることが好ましく、特に好ましくは０．３～１．５μｍである。具体的には、酸化チタン、硫酸バリウム、炭酸カルシウム、硫化亜鉛などの粒子状の白色顔料が好ましく、これらを混合しても良い。さらに、フィルム中に一般的に含有されている無機粒子、例えばシリカ、アルミナ、タルク、カオリン、クレー、リン酸カルシウム、雲母、ヘクトライト、ジルコニア、酸化タングステン、フッ化リチウム、フッ化カルシウム、硫酸カルシウムなどを併用しても良い。 The inorganic pigment contained in the first coating layer B1 and the second coating layer B2 is preferably in the form of particles, and the average particle diameter of the particles is preferably 0.1 to 4.0 μm, particularly preferably It is 0.3 to 1.5 μm. Specifically, particulate white pigments such as titanium oxide, barium sulfate, calcium carbonate, and zinc sulfide are preferred, and these may be mixed. Furthermore, inorganic particles commonly contained in films, such as silica, alumina, talc, kaolin, clay, calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, calcium sulfate, etc. May be used together.
　本発明の目的を満たすものであれば、粒子の形状は特に限定されるものでなく、球状粒子、不定形の球状でない粒子を使用できる。不定形の粒子の粒子径は円相当径として計算することができる。 The shape of the particles is not particularly limited as long as the object of the present invention is met, and spherical particles and irregularly shaped non-spherical particles can be used. The particle diameter of irregularly shaped particles can be calculated as a circular equivalent diameter.
　また、本発明の空洞含有ポリエステル系易接着フィルムには、印刷用インキやコーティング剤などの塗れ性や接着性を改良するために、その少なくとも片面に易接着性と帯電防止性を両立した機能性易接着層を設けることが好ましい。該機能性易接着層を構成する組成物に含ませる樹脂としては、ポリエステル樹脂、ポリカーボネート構造を有するウレタン樹脂、ポリエステルウレタン樹脂、アクリル樹脂などの通常のポリエステル系フィルムの接着性を向上させる手段として開示させている化合物が適用可能である。いわゆるインラインコーティングを容易にするために、樹脂は水溶性や水分散性のものが好ましい。 In addition, the cavity-containing polyester-based easy-adhesive film of the present invention has functionality that combines easy-adhesion and antistatic properties on at least one side of the film in order to improve the applicability and adhesion of printing inks and coating agents. It is preferable to provide an easily adhesive layer. The resin to be included in the composition constituting the functional adhesive layer includes polyester resin, urethane resin having a polycarbonate structure, polyester urethane resin, acrylic resin, etc. Disclosed as a means for improving the adhesion of ordinary polyester films. Compounds that have the following properties are applicable. In order to facilitate so-called in-line coating, the resin is preferably water-soluble or water-dispersible.
　本発明において、機能性易接着層を構成する組成物に架橋剤としてブロックイソシアネートを添加しても良い。３官能以上のブロックイソシアネートがさらに好ましく、４官能以上のブロックイソシアネートが特に好ましい。これらにより、後述する組成物に帯電防止剤を含ませた場合の易接着層表面の帯電防止性の制御及び、帯電防止剤の背面移行性を抑制させることが可能である。 In the present invention, a blocked isocyanate may be added as a crosslinking agent to the composition constituting the functional adhesive layer. Trifunctional or higher functional block isocyanates are more preferred, and tetrafunctional or higher functional block isocyanates are particularly preferred. By these means, it is possible to control the antistatic properties of the surface of the easily adhesive layer when an antistatic agent is included in the composition described below, and to suppress the migration of the antistatic agent to the back surface.
　本発明におけるブロックイソシアネートは、水溶性、または、水分散性を付与するために前駆体であるポリイソシアネートに親水基を導入することができる。親水基としては、（１）ジアルキルアミノアルコールの四級アンモニウム塩やジアルキルアミノアルキルアミンの四級アンモニウム塩など、（２）スルホン酸塩、カルボン酸塩、リン酸塩など、（３）アルキル基で片末端封鎖されたポリエチレングリコール、ポリプロピレングリコールなどが挙げられる。親水性部位を導入した場合は（１）カチオン性、（２）アニオン性、（３）ノニオン性となる。なかでも、他の水溶性樹脂はアニオン性のものが多いため、容易に相溶できるアニオン性やノニオン性が好ましい。また、アニオン性は他の樹脂との相溶性に優れ、ノニオン性はイオン性の親水基をもたないため、耐湿熱性を向上させるためにも好ましい。 In order to impart water solubility or water dispersibility to the blocked isocyanate in the present invention, a hydrophilic group can be introduced into the precursor polyisocyanate. Hydrophilic groups include (1) quaternary ammonium salts of dialkylamino alcohols and quaternary ammonium salts of dialkylaminoalkylamines, (2) sulfonates, carboxylates, phosphates, etc., and (3) alkyl groups. Examples include polyethylene glycol and polypropylene glycol with one end blocked. When a hydrophilic site is introduced, it becomes (1) cationic, (2) anionic, and (3) nonionic. Among these, since many other water-soluble resins are anionic, anionic or nonionic resins that are easily compatible are preferred. Furthermore, anionic resins have excellent compatibility with other resins, and nonionic resins do not have ionic hydrophilic groups, so they are preferable for improving moist heat resistance.
　アニオン性の親水基としては、ポリイソシアネートに導入するための水酸基、親水性を付与するためのカルボン酸基を有するものが好ましい。例えば、グリコール酸、乳酸、酒石酸、クエン酸、オキシ酪酸、オキシ吉草酸、ヒドロキシピバリン酸、ジメチロール酢酸、ジメチロールプロパン酸、ジメチロールブタン酸、カルボン酸基を有するポリカプロラクトンが挙げられる。カルボン酸基を中和するには、有機アミン化合物が好ましい。例えば、アンモニア、メチルアミン、エチルアミン、プロピルアミン、イソプロピルアミン、ブチルアミン、２－エチルヘキシルアミン、シクロヘキシルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジイソプロピルアミン、ジブチルアミン、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、エチレンジアミンなどの炭素数１から２０の直鎖状、分岐状の１，２または３級アミン、モルホリン、Ｎ－アルキルモルホリン、ピリジンなどの環状アミン、モノイソプロパノールアミン、メチルエタノールアミン、メチルイソプロパノールアミン、ジメチルエタノールアミン、ジイソプロパノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチルエタノールアミン、トリエタノールアミンなどの水酸基含有アミンなどが挙げられる。 As the anionic hydrophilic group, those having a hydroxyl group for introduction into the polyisocyanate and a carboxylic acid group for imparting hydrophilicity are preferred. Examples include glycolic acid, lactic acid, tartaric acid, citric acid, oxybutyric acid, oxyvaleric acid, hydroxypivalic acid, dimethylolacetic acid, dimethylolpropanoic acid, dimethylolbutanoic acid, and polycaprolactone having a carboxylic acid group. Organic amine compounds are preferred for neutralizing carboxylic acid groups. For example, ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, 2-ethylhexylamine, cyclohexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine , C1 to C20 linear, branched, or tertiary amines such as ethylenediamine, morpholine, N-alkylmorpholine, cyclic amines such as pyridine, monoisopropanolamine, methylethanolamine, methylisopropanolamine, Examples include hydroxyl group-containing amines such as dimethylethanolamine, diisopropanolamine, diethanolamine, triethanolamine, diethylethanolamine, and triethanolamine.
　ノニオン性の親水基としては、アルキル基で片末端封鎖されたポリエチレングリコール、ポリプロピレングリコールのエチレンオキサイドおよび／またはプロピレンオキサイドの繰り返し単位が３～５０が好ましく、より好ましくは、５～３０である。繰り返し単位が小さい場合は、樹脂との相溶性が悪くなり、ヘイズが上昇し、大きい場合は、高温高湿下の接着性が低下する場合がある。本発明のブロックイソシアネートは水分散性向上のために、ノニオン系、アニオン系、カチオン系、両性界面活性剤を添加することができる。例えばポリエチレングリコール、多価アルコール脂肪酸エステル等のノニオン系、脂肪酸塩、アルキル硫酸エステル、アルキルベンゼンスルホン酸塩、スルホコハク酸塩、アルキルリン酸塩等のアニオン系、アルキルアミン塩、アルキルベタイン等のカチオン系、カルボン酸アミン塩、スルホン酸アミン塩、硫酸エステル塩等の界面活性剤などが挙げられる。 The nonionic hydrophilic group preferably has 3 to 50, more preferably 5 to 30, repeating units of ethylene oxide and/or propylene oxide in polyethylene glycol or polypropylene glycol that is end-capped with an alkyl group. If the repeating unit is small, the compatibility with the resin will be poor and the haze will increase, and if the repeating unit is large, the adhesiveness under high temperature and high humidity may be reduced. Nonionic, anionic, cationic, or amphoteric surfactants may be added to the blocked isocyanate of the present invention to improve water dispersibility. For example, nonionic systems such as polyethylene glycol and polyhydric alcohol fatty acid esters, anionic systems such as fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, sulfosuccinates, and alkyl phosphates, cationic systems such as alkylamine salts, and alkyl betaines, Examples include surfactants such as carboxylic acid amine salts, sulfonic acid amine salts, and sulfuric acid ester salts.
　機能性易接着層を構成する組成物には帯電防止剤を添加することが好ましい。帯電防止剤は接触した他の物品やフィルム自体の背面への移行性を抑制できるものが好ましい。例えば官能基がソルビタン型、エーテル型、エステル型、ソルビトール型、グルコース型等のノニオン系、第４級アンモニウム塩型、第４級アンモニウム樹脂型、イミダゾリン型、アーコベル型、ソロミンＡ型等のカチオン系、アルキルサルフェート型、アルキルホスフェート型、リン酸エステル塩型、硫酸エステル塩型等のアニオン系およびベタイン型、アミノ酸型、アミノ硫酸エステル型等の両性系の界面活性剤タイプまたはポリマータイプ等が挙げられる。 It is preferable to add an antistatic agent to the composition constituting the functional adhesive layer. The antistatic agent is preferably one that can suppress migration to other articles with which it comes in contact or to the back side of the film itself. For example, the functional group is nonionic such as sorbitan type, ether type, ester type, sorbitol type, glucose type, cationic type such as quaternary ammonium salt type, quaternary ammonium resin type, imidazoline type, arcobel type, solomine A type, etc. , alkyl sulfate type, alkyl phosphate type, phosphate ester salt type, sulfate ester salt type, and other anionic surfactants, betaine type, amino acid type, amino sulfate ester type, and other amphoteric surfactant types or polymer types. .
　上記帯電防止剤において、４級アンモニウム塩基の対イオンとしては、アニオン性化合物であれば特に限定されるものではないが、好ましくはハロゲンイオン、モノもしくはポリハロゲン化アルキルイオン、ナイトレートイオン、サルフェートイオン、アルキルサルフェートイオン、スルホネートイオンまたはアルキルスルホネートイオンから適宜選択できるが、好ましくは表面固有抵抗値の安定性、塗液安定性、インキ密着性と、帯電防止剤の他の物品や背面への移行性を抑制させるにはエトサルフェート塩が好ましい。 In the above antistatic agent, the counter ion of the quaternary ammonium base is not particularly limited as long as it is an anionic compound, but preferably a halogen ion, a mono- or polyhalogenated alkyl ion, a nitrate ion, or a sulfate ion. , alkyl sulfate ion, sulfonate ion, or alkyl sulfonate ion, but preferably the stability of surface resistivity value, stability of coating liquid, ink adhesion, and migration of antistatic agent to other articles or back surface. Ethosulfate salts are preferred in order to suppress this.
（ポリカーボネートウレタン樹脂）
　本発明において機能性易接着層を構成する組成物に好ましく含有されるポリカーボネート構造を有するウレタン樹脂は、少なくともポリカーボネートポリオール成分とポリイソシアネート成分に由来するウレタン結合部分構造を有することが好ましく、さらに必要に応じて鎖延長剤を含むものである。さらに分岐構造を有するポリイソシアネートを、分子鎖を構成する前記のようないずれかの原料成分の末端官能基数が３個以上存在することによって、合成、重合された後に枝分かれ上の分子鎖構造を形成することによって好適に導入されるものであることが好ましい。 (Polycarbonate urethane resin)
In the present invention, the urethane resin having a polycarbonate structure preferably contained in the composition constituting the functional adhesive layer preferably has a urethane bonding partial structure derived from at least a polycarbonate polyol component and a polyisocyanate component. Depending on the situation, a chain extender may be included. Furthermore, the polyisocyanate having a branched structure is synthesized and polymerized by the presence of three or more terminal functional groups of any of the above-mentioned raw materials constituting the molecular chain to form a branched molecular chain structure. It is preferable that it be suitably introduced by.
　本発明におけるポリカーボネート構造を有するウレタン樹脂、且つ分岐構造を有する場合のウレタン樹脂は、その分岐構造によって、分子鎖中の末端官能基数の下限は好ましくは３個であり、さらに好ましくは４個である。３個以上であると、水付着時のブロッキング耐性を向上できて好ましい。本発明におけるポリカーボネート構造を有するウレタン樹脂は、その分岐構造によって、分子鎖中の末端官能基数の上限は好ましくは６個である。６個以下であると、樹脂を水溶液中に安定して分散できて好ましい。 In the urethane resin having a polycarbonate structure in the present invention, and the urethane resin having a branched structure, 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. . It is preferable that the number is 3 or more because blocking resistance when attached to water can be improved. In the urethane resin having a polycarbonate structure in the present invention, the upper limit of the number of terminal functional groups in the molecular chain 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.
　本発明におけるポリカーボネート構造を有するウレタン樹脂を重合するために用いるポリカーボネートポリオール成分には、耐熱、耐加水分解性に優れる脂肪族系ポリカーボネートポリオールを含有することが好ましい。脂肪族系ポリカーボネートポリオールとしては、脂肪族系ポリカーボネートジオール、脂肪族系ポリカーボネートトリオールなどが挙げられるが、好適には脂肪族系ポリカーボネートジオールを用いることができる。本発明におけるポリカーボネート構造を有するウレタン樹脂を重合するために用いる脂肪族系ポリカーボネートジオールとしては、例えば、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、１，８－ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコールなどのジオール類の１種または２種以上と、例えば、ジメチルカーボネート、エチレンカーボネート、ホスゲンなどのカーボネート類とを反応させることにより得られる脂肪族系ポリカーボネートジオールなどが挙げられる。 The polycarbonate polyol component used to polymerize the urethane resin having a polycarbonate structure in the present invention preferably contains an aliphatic polycarbonate polyol that has excellent heat resistance and hydrolysis resistance. Examples of aliphatic polycarbonate polyols include aliphatic polycarbonate diols and aliphatic polycarbonate triols, and aliphatic polycarbonate diols can be preferably used. Examples of the aliphatic polycarbonate diol used for 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-pentane diol. Diol, one type of diol such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, etc. Alternatively, examples include aliphatic polycarbonate diols obtained by reacting two or more types with carbonates such as dimethyl carbonate, ethylene carbonate, and phosgene.
　機能性易接着層には、表面に滑り性やマット性、インキ吸収性などを付与するために、滑剤粒子を含むこともできる。粒子は、無機粒子であっても、有機粒子であってもよく、特に限定されるものではないが、（１）シリカ、カオリナイト、タルク、軽質炭酸カルシウム、重質炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、カーボンブラック、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、酸化ジルコニウム、二酸化チタン、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、水酸化アルミニウム、炭酸カルシウム、炭酸マグネシウム、リン酸カルシウム、水酸化マグネシウム、硫酸バリウム等の無機粒子、（２）アクリルあるいはメタアクリル系、塩化ビニル系、酢酸ビニル系、ナイロン、スチレン／アクリル系、スチレン／ブタジエン系、ポリスチレン／アクリル系、ポリスチレン／イソプレン系、ポリスチレン／イソプレン系、メチルメタアクリレート／ブチルメタアクリレート系、メラミン系、ポリカーボネート系、尿素系、エポキシ系、ウレタン系、フェノール系、ジアリルフタレート系、ポリエステル系等の有機粒子が挙げられるが、易接着層に適度な滑り性を与えるために、シリカが特に好ましく使用される。 The functional adhesive layer can also contain lubricant particles in order to impart slipperiness, matte properties, ink absorption properties, etc. to the surface. Particles may be inorganic particles or organic particles, and are not particularly limited, but 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 / Organic particles such as butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, polyester, etc. are used, but in order to give the easy-adhesion layer appropriate slipperiness. Silica is particularly preferably used.
　前記の粒子の平均粒子径は、０．１～２．４μｍが好ましく、さらに好ましくは０．３～２．０μｍである。粒子の平均粒子径が０．１μｍ以下であると、フィルム表面の光沢度が上昇する可能性がある。逆に、２．４μｍを越えると、粒子が機能性易接着層から脱落し、粉落ちの原因になる傾向がある。  The average particle diameter of the particles is preferably 0.1 to 2.4 μm, more preferably 0.3 to 2.0 μm. If the average particle diameter of the particles is 0.1 μm or less, the glossiness of the film surface may increase. On the other hand, if the particle size exceeds 2.4 μm, the particles tend to fall off from the functional adhesion layer, causing powder falling.​
　前記の粒子の含有量は、本発明の効果を阻害しない範囲において添加することが可能であるが、粒子が機能性易接着層から脱落し、粉落ちを起こさないようにするため、粒子の含有量は、機能性易接着層固形分全体に対して、粒子の固形分が０～７０．０質量％であることが好ましく、０～６０．０質量％であることが好ましく、さらに０～５５．０質量％であることが好ましい。 The content of the particles can be added within a range that does not impede the effects of the present invention, but in order to prevent the particles from falling off the functional adhesive layer and causing powder falling, the content of the particles should be adjusted to a level that does not impede the effects of the present invention. The solid content of the particles is preferably 0 to 70.0% by mass, preferably 0 to 60.0% by mass, and more preferably 0 to 55% by mass, based on the entire solid content of the functional adhesive layer. Preferably, it is .0% by mass.
　本発明の目的を満たすものであれば、粒子の形状は特に限定されるものでなく、球状粒子、不定形の球状でない粒子を使用できる。不定形の粒子の粒子径は円相当径として計算することができる。 The shape of the particles is not particularly limited as long as the object of the present invention is met, and spherical particles and irregularly shaped non-spherical particles can be used. The particle diameter of irregularly shaped particles can be calculated as a circular equivalent diameter.
（ポリエステル樹脂）
　本発明における機能性易接着層を形成する組成物に好ましく含ませることができるポリエステル樹脂は、直鎖状のものであってもよいが、より好ましくは、ジカルボン酸と、分岐構造を有するジオールとを構成成分とするポリエステル樹脂であることが好ましい。ここで言うジカルボン酸は、その主成分がテレフタル酸、イソフタル酸又は２，６－ナフタレンジカルボン酸である他、アジピン酸、セバシン酸等の脂肪族ジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸等の芳香族ジカルボン酸が、挙げられる。また、分岐したグリコールとは枝分かれしたアルキル基を有するジオールであって、例えば、２，２－ジメチル－１，３－プロパンジオール、２－メチル－２－エチル－１，３－プロパンジオール、２－メチル－２－ブチル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２－メチル－２－イソプロピル－１，３－プロパンジオール、２－メチル－２－ｎ－ヘキシル－１，３－プロパンジオール、２，２－ジエチル－１，３－プロパンジオール、２－エチル－２－ｎ－ブチル－１，３－プロパンジオール、２－エチル－２－ｎ－ヘキシル－１，３－プロパンジオール、２，２－ジ－ｎ－ブチル－１，３－プロパンジオール、２－ｎ－ブチル－２－プロピル－１，３－プロパンジオール、及び２，２－ジ－ｎ－ヘキシル－１，３－プロパンジオールなどが挙げられる。 (polyester resin)
The polyester resin that can be preferably included in the composition forming the functional adhesive layer in the present invention may be a linear one, but more preferably a dicarboxylic acid and a diol having a branched structure. It is preferable that it is a polyester resin having as a constituent component. The dicarboxylic acids mentioned here are 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, and dicarboxylic acids. , 6-naphthalene dicarboxylic acid and the like. Further, 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-propanediol, and 2,2-di-n- Examples include hexyl-1,3-propanediol.
　上記ポリエステル樹脂は、上記のより好ましい態様である分岐したグリコール成分は全グリコール成分の中に、好ましくは１０モル％以上の割合で、さらに好ましくは２０モル％以上の割合で含有されるものと言える。１０モル％以上であると、結晶性が高くなり過ぎず、易接着層の接着性が良好となり好ましい。全グリコール成分の中のグリコール成分上限は、好ましくは８０モル％以下であり、より好ましくは７０質量％である。８０モル％以下であると、副生成物であるオリゴマー濃度が抑制され、易接着層の透明性が良好であり好ましい。上記化合物以外のグリコール成分としてはエチレングリコールが最も好ましい。少量であれば、ジエチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオールまたは１，４－シクロヘキサンジメタノールなどを用いても良い。 In the above-mentioned polyester resin, the branched glycol component, which is the more preferred embodiment, is preferably contained in a proportion of 10 mol% or more, more preferably 20 mol% or more, in the total glycol component. . When the content is 10 mol% or more, the crystallinity does not become too high and the adhesion of the easily bonding layer becomes good, which is preferable. The upper limit of the glycol component in all glycol components is preferably 80 mol% or less, more preferably 70% by mass. When it is 80 mol% or less, the concentration of oligomers which are by-products is suppressed, and the transparency of the easily bonding layer is good, which is preferable. Ethylene glycol is most preferred as a glycol component other than the above compounds. If the amount is small, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol, or the like may be used.
　上記ポリエステル樹脂の構成成分としてのジカルボン酸としては、テレフタル酸又はイソフタル酸であるのが最も好ましい。上記ジカルボン酸の他に、共重合ポリエステル系樹脂に水分散性を付与させるため、５－スルホイソフタル酸等を１～１０モル％の値囲で共重合させるのが好ましく、例えば、５－スルホイソフタル酸ジメチル等を挙げることができる。ナフタレン骨格を有するジカルボン酸を含有するポリエステル樹脂を使用してもよいが、ＵＶインキへの密着性の低下を抑制するために、その量的割合は全カルボン酸成分中で５モル％以下であることが好ましく、使用しなくともよい。 The dicarboxylic acid as a component of the polyester resin is most preferably terephthalic acid or isophthalic acid. In addition to the dicarboxylic acids mentioned above, in order to impart water dispersibility to the copolymerized polyester resin, it is preferable to copolymerize 5-sulfoisophthalic acid or the like in a range of 1 to 10 mol%, such as 5-sulfoisophthalic acid. Examples include dimethyl acid. A polyester resin containing a dicarboxylic acid having a naphthalene skeleton may be used, but its quantitative proportion is 5 mol% or less in the total carboxylic acid component in order to suppress a decrease in adhesion to UV ink. is preferable, and may not be used.
　上記ポリエステル樹脂の構成成分として、ポリエステル樹脂としての特性が損なわれない程度にトリオールやトリカルボン酸を含まれても構わない。 As a component of the polyester resin, triol or tricarboxylic acid may be included to the extent that the properties as a polyester resin are not impaired.
　上記ポリエステル樹脂は、カルボキシル基以外の極性基を含有してもよい。例えば、スルホン酸金属塩基、リン酸基等が挙げられるが、これらは１種又は２種以上有することができる。スルホン酸金属塩基を導入する方法としては、５?スルホイソフタル酸、４?スルホナフタレン?２，７?ジカルボン酸、５?〔４?スルホフェノキシ〕イソフタル酸等の金属塩又は２?スルホ?１，４?ブタンジオ?ル、２，５?ジメチル?３?スルホ?２，５?ヘキサンジオ?ル等の金属塩等のスルホン酸金属塩基を含有するジカルボン酸又はグリコ?ルをポリカルボン酸成分またはポリオール成分の合計の１０モル％以下、好ましくは７モル％以下、更に好ましくは５モル％以下の範囲で使用する方法が挙げられる。１０モル％を超えると樹脂自体の耐加水分解性、塗膜の耐水性が低下する傾向にある。 The above polyester resin may contain polar groups other than carboxyl groups. Examples include sulfonic acid metal bases, phosphoric acid groups, etc., and one or more types of these can be used. Methods for introducing the sulfonic acid metal base include metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-[4-sulfophenoxy]isophthalic acid, or 2-sulfo-1, A dicarboxylic acid or glycol containing a sulfonic acid metal base such as a metal salt such as 4-butanediol, 2,5-dimethyl, 3-sulfo-2,5-hexanediol is used as a polycarboxylic acid component or a polyol component. Examples include a method in which the amount is 10 mol % or less, preferably 7 mol % or less, and more preferably 5 mol % or less of the total amount. If it exceeds 10 mol%, the hydrolysis resistance of the resin itself and the water resistance of the coating film tend to decrease.
　密着性を向上させる手段として他の開示させている化合物が適用添加可能である。機能性易接着層の密着耐久性を向上させるために他の架橋剤であっても、高温高湿下での密着性を更に向上させることが可能になる。具体的な架橋剤としては、尿素系、エポキシ系、メラミン系、オキサゾリン系、カルボジイミド系等が挙げられる。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用することができる。 Other disclosed compounds can be added as a means to improve adhesion. Even if other crosslinking agents are used to improve the adhesion durability of the functional adhesive layer, it is possible to further improve the adhesion under high temperature and high humidity. Specific crosslinking agents include urea-based, epoxy-based, melamine-based, oxazoline-based, carbodiimide-based, and the like. Further, in order to promote the crosslinking reaction, a catalyst or the like can be appropriately used as necessary.
（添加剤）
　本発明における機能性易接着層中には、本発明の効果を阻害しない範囲において公知の添加剤、例えば界面活性剤、Ｐｈ調整剤、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の粒子、核剤等を添加しても良い。 (Additive)
In the functional adhesive layer of the present invention, known additives such as surfactants, pH adjusters, antioxidants, heat stabilizers, weather stabilizers, and ultraviolet absorbers may be added to the extent that they do not impede the effects of the present invention. , organic lubricants, pigments, dyes, organic or inorganic particles, nucleating agents, etc. may be added.
　機能性易接着層を設ける方法としては、グラビアコート方式、キスコート方式、ディップ方式、スプレイコート方式、カーテンコート方式、エアナイフコート方式、ブレードコート方式、リバースロールコート方式など通常用いられている方法が適用できる。塗布する段階としては、フィルムの延伸前に塗布する方法、縦延伸後に塗布する方法、延伸処理の終了したフィルム表面に塗布する方法などのいずれの方法も可能である。 As a method for providing a functional adhesive layer, commonly used methods such as gravure coating, kiss coating, dip coating, spray coating, curtain coating, air knife coating, blade coating, and reverse roll coating are applicable. can. The coating step can be carried out by any method such as coating before stretching the film, coating after longitudinal stretching, or coating on the surface of the film after stretching.
　本発明における空洞含有ポリエステル系易接着フィルムの製造方法について説明する。例えば、ポリエステル樹脂とポリプロピレン樹脂とシリコーン樹脂を含有する組成物からなる混合ペレットを乾燥した後、Ｔ字の口金からシート状に溶融押出し、静電印加法などにより、キャスティングドラムに密着させ冷却固化し、未延伸フィルムを得る。
　次いで、該未延伸フィルムを延伸・配向処理するが、以下では、最も一般的に用いられる逐次二軸延伸方法、特に未延伸フィルムを長手方向に縦延伸し、次いで幅方向に横延伸する方法を例に説明する。まず、長手方向への縦延伸工程では、フィルムを加熱し、周速が異なる２本あるいは多数本のロール間で２．５～５．０倍に延伸する。このときの加熱手段としては、加熱ロールを用いる方法でも非接触の加熱媒体を用いる方法でもよく、これらを併用してもよい。この際、フィルムの温度を（Ｔｇ－１０℃）～（Ｔｇ＋５０℃）の範囲とすることが好ましい。次いで１軸延伸フィルムをリバースグラビアコート法によりＷＥＴ塗工量が１～２０ｇ／ｍ２になるように塗布した後、テンターに導入し、幅方向に（Ｔｇ－１０℃）～Ｔｍ－１０℃以下の温度で２．５～５倍に延伸することで２軸延伸フィルムが得られる。
　ここで、Ｔｇはポリエステル樹脂のガラス転移温度、Ｔｍはポリエステルの融点である。また上記より得られるフィルムに対し、必要に応じて熱処理を施すことが好ましく、処理温度としては（Ｔｍ－６０℃）～Ｔｍの範囲で行うのが好ましい。 A method for producing a hollow polyester easily adhesive film according to the present invention will be explained. For example, after drying a mixed pellet consisting of a composition containing a polyester resin, a polypropylene resin, and a silicone resin, it is melt-extruded into a sheet form from a T-shaped nozzle, and is brought into close contact with a casting drum using an electrostatic application method and cooled to solidify. , to obtain an unstretched film.
Next, the unstretched film is stretched and oriented. In the following, the most commonly used sequential biaxial stretching method, particularly a method in which the unstretched film is longitudinally stretched in the longitudinal direction and then transversely stretched in the width direction, will be described. Let's explain with an example. First, in the longitudinal stretching step, the film is heated and stretched by 2.5 to 5.0 times between two or multiple rolls having different circumferential speeds. The heating means at this time may be a method using a heating roll or a method using a non-contact heating medium, or a combination of these methods may be used. At this time, it is preferable that the temperature of the film is in the range of (Tg-10°C) to (Tg+50°C). Next, the uniaxially stretched film was applied by reverse gravure coating so that the wet coating amount was 1 to 20 g/m 2 , and then introduced into a tenter and coated in the width direction from (Tg - 10°C) to Tm - 10°C or less. A biaxially stretched film can be obtained by stretching 2.5 to 5 times at a temperature of .
Here, Tg is the glass transition temperature of the polyester resin, and Tm is the melting point of the polyester. Further, it is preferable that the film obtained above is subjected to heat treatment if necessary, and the treatment temperature is preferably in the range of (Tm-60°C) to Tm.
　また、本発明における空洞含有ポリエステル系易接着フィルムは、使用済みの本発明の空洞含有ポリエステル系易接着フィルムからなる回収原料を空洞含有層Ａに含有することも可能である。使用済みの本発明の空洞含有ポリエステル系易接着フィルムとは、製膜工程で発生した耳部や破断トラブルなどで生じた屑フィルムや市中から回収したものである。空洞含有層Ａに回収原料を加える場合においても、本発明の空洞含有ポリエステル系易接着フィルムの回収原料を使用すれば、ポリプロピレン樹脂にシリコーン樹脂を少量添加しているので、空洞発現性を維持できる。これにより空洞含有ポリエステル系易接着フィルムは、十分な軽量性やクッション性が得られ、かつ隠蔽性や白色度に優れた空洞含有ポリエステル系易接着フィルムを得ることができる。特に、環境負荷対応が求められている今日においては、使用済みの空洞含有ポリエステル系易接着フィルムをマテリアルリサイクルするため、回収原料の添加量が従来よりも増加する。しかし、シリコーン樹脂を添加すれば、添加量の増加した場合においても空洞発現性を維持できる。 Further, the cavity-containing polyester-based easily adhesive film of the present invention can also contain, in the cavity-containing layer A, a recovered raw material made of the used cavity-containing polyester-based easily adhesive film of the present invention. The used hollow-containing polyester-based easily adhesive film of the present invention is a scrap film generated from edges or breakage troubles that occurred during the film forming process, or one that is collected from the market. Even when adding recovered raw materials to the cavity-containing layer A, if the recovered raw materials of the cavity-containing polyester-based easily adhesive film of the present invention are used, the cavity development property can be maintained because a small amount of silicone resin is added to the polypropylene resin. . As a result, it is possible to obtain a cavity-containing polyester-based easily adhesive film that has sufficient lightness and cushioning properties, and has excellent hiding properties and whiteness. In particular, in today's world where there is a need to reduce environmental impact, the amount of recovered raw materials added is increased compared to the past because used hollow polyester adhesive films are recycled. However, if a silicone resin is added, the cavity development property can be maintained even when the amount added is increased.
　回収原料の添加量としては、原料コスト低減、白色度および製膜性の観点から、空洞含有層Ａの全質量１００質量％に対して、５～７０質量％が好ましい。
　なお、第１被覆層Ｂ１又は第２被覆層Ｂ２が回収原料を含有してもかまわないが、白色度の悪化および回収原料中のポリプロピレン樹脂の露出の観点から、含有しないことが好ましい。 The amount of the recovered raw material added is preferably 5 to 70% by mass based on 100% by mass of the total mass of the cavity-containing layer A, from the viewpoints of raw material cost reduction, whiteness, and film formability.
Although the first coating layer B1 or the second coating layer B2 may contain the recovered raw material, it is preferable not to contain it from the viewpoint of deterioration of whiteness and exposure of the polypropylene resin in the recovered raw material.
　本発明における空洞含有ポリエステル系易接着フィルムの見かけ密度は、０．８０ｇ／ｃｍ３以上１．２ｇ／ｃｍ３以下であることが好ましく、０．８０ｇ／ｃｍ３以上１．１０ｇ／ｃｍ３以下がより好ましい。見かけ密度が０．８０ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下である場合、空洞含有ポリエステル系易接着フィルム中に占める全空洞が適量となり、印刷加工などの後加工時や使用時において、取り扱い易くなる。また、見かけ密度が０．８０ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下である場合、十分な軽量性やクッション性が得られる。
　特に本発明における空洞含有ポリエステル系易接着フィルムは、シリコーン樹脂を微量含有することで、見かけ密度が０．８０～１．１０であっても優れた軽量性、製膜性、隠蔽性及び白色度を有する。 The apparent density of the cavity-containing polyester easily adhesive film in the present invention is preferably 0.80 g/cm 3 or more and 1.2 g/cm 3 or less, and preferably 0.80 g/cm 3 or more and 1.10 g/cm 3 or less. More preferred. When the apparent density is 0.80 g/cm3 or more and 1.20 g/ cm3 or less, the total amount of cavities in the void-containing polyester easy-adhesive film becomes an appropriate amount, making it difficult to handle during post-processing such as printing or during use. It becomes easier. Further, when the apparent density is 0.80 g/cm 3 or more and 1.20 g/cm 3 or less, sufficient lightness and cushioning properties can be obtained.
In particular, the cavity-containing polyester-based easily adhesive film of the present invention contains a small amount of silicone resin, so it has excellent lightness, film formability, hiding property, and whiteness even when the apparent density is 0.80 to 1.10. has.
　尚、見かけ密度は、後述の評価方法にて記載した測定法より得られる値である。 Incidentally, the apparent density is a value obtained by the measurement method described in the evaluation method described below.
　本発明における空洞含有ポリエステル系易接着フィルムは、全光線透過率が３０％以下であることが好ましく、２５％以下がより好ましい。全光線透過率が３０％以下である場合、十分な隠蔽性が得られる。例えばラベルなどに用いた場合、ラベルに印刷された画像が鮮明になる。尚、全光線透過率は、後述の評価方法にて記載した測定方法より得られる厚み５０μｍ換算での値である。 The cavity-containing polyester easily adhesive film of the present invention preferably has a total light transmittance of 30% or less, more preferably 25% or less. When the total light transmittance is 30% or less, sufficient hiding performance can be obtained. For example, when used on labels, the images printed on the labels become clearer. Incidentally, the total light transmittance is a value obtained in terms of a thickness of 50 μm obtained by the measurement method described in the evaluation method described below.
　本発明における空洞含有ポリエステル系易接着フィルムは、色調ｂ値が４．０以下であることが好ましく、更に好ましくは３．０以下であり、特に好ましくは１．５以下である。色調ｂ値が４．０よりも大きい場合、白色度が劣り、ラベルなどにした場合、印刷時の鮮明性が落ち、商品価値を損ねるおそれがある。 The cavity-containing polyester easily adhesive film of the present invention preferably has a color tone b value of 4.0 or less, more preferably 3.0 or less, particularly preferably 1.5 or less. If the color tone b value is greater than 4.0, the whiteness will be poor, and when printed on labels, etc., the clarity during printing may deteriorate, and the product value may be impaired.
　本発明の空洞含有ポリエステル系易接着フィルムの厚みは任意であるが、２０μｍ以上３００μｍ以下であることが好ましい。 Although the thickness of the cavity-containing polyester easily adhesive film of the present invention is arbitrary, it is preferably 20 μm or more and 300 μm or less.
　本発明において、機能性易接着層は、後述の評価方法による硬化型インキ印刷層との密着残存面積が、全体の９０％以上であることが好ましく、９９％以上であることが更に好ましい。もちろん、最も好ましくは１００％である。 In the present invention, the functional adhesive layer preferably has a residual area in close contact with the curable ink printed layer by the evaluation method described below of 90% or more of the total, and more preferably 99% or more. Of course, the most preferable value is 100%.
　機能性易接着層は、上述のように帯電防止剤を含有していることが好ましく、表面固有抵抗値が１．０×１０１３Ω／ｓｑ以下であることが好ましい。更に好ましくは１．０×１０１２Ω／ｓｑ以下、特に好ましくは１．０×１０１１Ω／ｓｑ以下である。下限は特に設けないが、１．０×１０５Ω／ｓｑ以上であっても好ましく、１．０×１０６Ω／ｓｑ以上であっても好ましい。 The functional adhesive layer preferably contains an antistatic agent as described above, and preferably has a surface resistivity of 1.0×10 13 Ω/sq or less. More preferably, it is 1.0×10 12 Ω/sq or less, particularly preferably 1.0×10 11 Ω/sq or less. There is no particular lower limit, but it is preferably 1.0×10 5 Ω/sq or more, and preferably 1.0×10 6 Ω/sq or more.
　機能性易接着層は、後述の評価方法によるピンホール状ハジキ個数が５個／ｍ２以下であることが好ましい。ピンホール状ハジキ個数は少ないほど好ましく、最も好ましくはもちろん０個／ｍ２である。 The functional adhesive layer preferably has a pinhole-like repellency number of 5 pieces/m 2 or less according to the evaluation method described below. It is preferable that the number of pinhole-like repellents is as small as possible, and of course, the most preferable is 0 pieces/m 2 .
　本発明の空洞含有ポリエステル系易接着フィルムの機能性易接着層は、１５０℃３０分加熱後の水接触角が５０～９０°であることが好ましい。更には５５～８５°が好ましい。この水接触角が９０°以下である場合、空洞含有ポリエステル系易接着フィルムは、加工工程でのコーティング抜けや印刷抜けを抑制することができる。この水接触角は小さいことが好ましいが、ポリエステル樹脂を含ませている場合には、５０°以上であっても好ましい。また、機能性易接着層の１５０℃３０分加熱後によるジヨードメタンの接触角が１０～６０°であることが好ましい。ジヨードメタンの接触角が６０°以下である場合、空洞含有ポリエステル系易接着フィルムは、加工工程でのコーティング抜けや印刷抜けを抑制することができる。ジヨードメタンの接触角が１０°以上である場合、空洞含有ポリエステル系易接着フィルムは、加工工程のコーティングと原反の密着性を向上させることができる。 The functional adhesive layer of the cavity-containing polyester adhesive film of the present invention preferably has a water contact angle of 50 to 90° after heating at 150°C for 30 minutes. More preferably, the angle is between 55° and 85°. When this water contact angle is 90 degrees or less, the hollow polyester-based easily adhesive film can suppress coating omissions and printing omissions during processing steps. This water contact angle is preferably small, but if a polyester resin is included, it is also preferably 50° or more. Further, it is preferable that the contact angle of diiodomethane after heating the functional adhesive layer at 150° C. for 30 minutes is 10 to 60°. When the contact angle of diiodomethane is 60° or less, the cavity-containing polyester-based easily adhesive film can suppress coating omissions and printing omissions during processing steps. When the contact angle of diiodomethane is 10° or more, the cavity-containing polyester-based easily adhesive film can improve the adhesion between the coating and the original fabric in the processing process.
　本発明の空洞含有ポリエステル系易接着フィルムの機能性易接着層は、８５℃８５％ＲＨ７２時間後の水接触角が４６～９０°であることが好ましい。更には５０～８５°が好ましい。この水接触角が９０°以下である場合、空洞含有ポリエステル系易接着フィルムは、長期倉庫保管後に加工する際に、コーティング抜けや印刷抜けを抑制することができる。この水接触角は小さいことが好ましいが、ポリエステル樹脂を含ませている場合には、４６°以上であっても好ましい。また、機能性易接着層の８５℃８５％ＲＨ７２時間後のジヨードメタンの接触角が１０～６０°であることが好ましい。ジヨードメタンの接触角が６０°以下である場合、空洞含有ポリエステル系易接着フィルムは、長期倉庫保管後に加工する際に、コーティング抜けや印刷抜けを抑制することができる。ジヨードメタンの接触角が１０°以上である場合、空洞含有ポリエステル系易接着フィルムは、加工工程のコーティングと原反の密着性を向上させることができる。 The functional adhesive layer of the hollow polyester adhesive film of the present invention preferably has a water contact angle of 46 to 90° after 72 hours at 85° C. and 85% RH. More preferably, the angle is 50° to 85°. When this water contact angle is 90 degrees or less, the hollow polyester-based easily adhesive film can suppress coating omission and printing omission when processed after long-term storage in a warehouse. This water contact angle is preferably small, but if a polyester resin is included, it is also preferably 46° or more. Further, it is preferable that the contact angle of diiodomethane of the functional adhesive layer after 72 hours at 85° C. and 85% RH is 10 to 60°. When the contact angle of diiodomethane is 60° or less, the void-containing polyester-based easily adhesive film can suppress coating omission and printing omission when processed after long-term storage in a warehouse. When the contact angle of diiodomethane is 10° or more, the cavity-containing polyester-based easily adhesive film can improve the adhesion between the coating and the original fabric in the processing process.
　以上より、本発明に係る空洞含有ポリエステル系易接着フィルムは、空洞含有層Ａがシリコーン樹脂を微量含有することで例えば加工工程においてポリプロピレン樹脂の熱劣化を抑制でき空洞発現性を維持できる。そのため、本発明に係る空洞含有ポリエステル系易接着フィルムは、見かけ密度が０．８０～１．２０であっても優れた軽量性、製膜性、隠蔽性及び白色度を有する。 From the above, in the cavity-containing polyester-based easy-adhesive film according to the present invention, since the cavity-containing layer A contains a small amount of silicone resin, thermal deterioration of the polypropylene resin can be suppressed, for example, in the processing process, and cavity development can be maintained. Therefore, the cavity-containing polyester-based easily adhesive film according to the present invention has excellent lightness, film-forming properties, hiding properties, and whiteness even if the apparent density is 0.80 to 1.20.
　よって、本発明に係る空洞含有ポリエステル系易接着フィルムは、ラベル、カード、包装材料、偏光板や積層セラミックコンデンサ製造時等に使用する離型フィルムなどの基材用途として好適に用いられる。 Therefore, the cavity-containing polyester easily adhesive film according to the present invention is suitably used as a base material for labels, cards, packaging materials, polarizing plates, release films used in the production of multilayer ceramic capacitors, and the like.
　以下に実施例を挙げて本発明を具体的に説明する。なお、本発明は以下に述べる実施例に限定されない。なお、実施例および比較例における各評価項目は次の方法で測定した。
（１）製膜性
　後述の空洞含有ポリエステル系易接着フィルム作製において記載する製膜条件で、製膜時間２時間で製造したときの破断回数で以下の通り評価を行った。
　　○：破断なし
　　△：１～３回破断
　　×：４回以上破断し、製膜不可 The present invention will be specifically described below with reference to Examples. Note that the present invention is not limited to the embodiments described below. In addition, each evaluation item in Examples and Comparative Examples was measured by the following method.
(1) Film-forming property The film-forming property was evaluated as follows based on the number of breaks when the film was produced for 2 hours under the film-forming conditions described in the production of a hollow-containing polyester-based easily adhesive film described below.
○: No breakage △: Broken 1 to 3 times ×: Broken 4 or more times, film formation not possible
（２）見かけ密度
　空洞含有ポリエステル系易接着フィルムを５．０ｃｍ四方の正方形に４枚切り出し、４枚を重ね合わせマイクロメーターを用いて有効数字４桁で、総厚みの場所を変えて１０点測定し、４枚重ね合わせた厚みの平均値を求めた。この平均値を４で除して有効数字３桁に丸め、一枚あたりの平均厚み（ｔ：μｍ）とした。同試料４枚の質量（ｗ：ｇ）を有効数字４桁で自動上皿天秤を用いて測定し、次式より見かけ密度を求めた。なお、見かけ密度は有効数字３桁に丸めた。
　見かけ密度（ｇ／ｃｍ３）＝ｗ／（５．０×５．０×ｔ×１０－４×４） (2) Apparent Density Cut out four 5.0 cm square pieces of hollow polyester adhesive film, stack the four pieces together, and measure the total thickness at 10 different locations using a micrometer to four significant digits. Then, the average value of the thickness of the four stacked sheets was determined. This average value was divided by 4 and rounded to three significant digits to obtain the average thickness per sheet (t: μm). The mass (w:g) of the four samples was measured using an automatic balance with four significant figures, and the apparent density was determined from the following formula. Note that the apparent density was rounded to three significant digits.
Apparent density (g/cm 3 ) = w/(5.0 x 5.0 x t x 10 -4 x 4)
（３）全光線透過率
　ヘイズメーター（日本電色工業社製、NDH5000）を用いて測定し,フィルム厚み５０μｍ当たりの値に換算した。同様の測定を３回行い、その算術平均値を採用した。 (3) Total light transmittance Measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH5000), and converted to a value per 50 μm of film thickness. Similar measurements were performed three times, and the arithmetic mean value was used.
（４）色調ｂ値
　色調ｂ値は、日本電色社製色差計（ＺＥ６０００）を用いて、ＪＩＳ－８７２２により測定した。色調ｂ値が小さい程、白色度が高く、黄色味が弱いと判断する。 (4) Color tone b value The color tone b value was measured according to JIS-8722 using a color difference meter (ZE6000) manufactured by Nippon Denshoku Co., Ltd. It is determined that the smaller the color tone b value, the higher the whiteness and the weaker the yellowish tinge.
（５）１５０℃３０分加熱後の水接触角
　ギアオーブンで１５０°の雰囲気下で試料を３０分加熱後、ＦＡＣＥ接触角計（協和界面化学株式会社製、ＣＡ－Ｘ型）を用いて、機能性易接着層表面の滴下１分後における蒸留水との接触角を測定した。なお、各試料につき５回測定を行い、測定値の最大値、最小値を除いた３つの測定値の平均値を接触角とした。 (5) Water contact angle after heating at 150°C for 30 minutes After heating the sample in a gear oven at 150° for 30 minutes, using a FACE contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model CA-X), The contact angle with distilled water on the surface of the functional adhesive layer 1 minute after dropping was measured. Note that each sample was measured five times, and the average value of the three measured values excluding the maximum and minimum measured values was taken as the contact angle.
（６）１５０℃３０分加熱後のジヨードメタン接触角
　ギアオーブンで１５０°の雰囲気下で試料を３０分加熱後、ＦＡＣＥ接触角計（協和界面化学株式会社製、ＣＡ－Ｘ型）を用いて、機能性易接着層表面の滴下１分後におけるジヨードメタンとの接触角を測定した。なお、各試料につき５回測定を行い、測定値の最大値、最小値を除いた３つの測定値の平均値を接触角とした。 (6) Diiodomethane contact angle after heating at 150°C for 30 minutes After heating the sample in a gear oven at 150° for 30 minutes, using a FACE contact angle meter (manufactured by Kyowa Kaimen Kagaku Co., Ltd., model CA-X), The contact angle with diiodomethane on the surface of the functional adhesive layer 1 minute after dropping was measured. Note that each sample was measured five times, and the average value of the three measured values excluding the maximum and minimum measured values was taken as the contact angle.
（７）８５℃８５％RH７２時間後の水接触角
　恒温恒湿機で８５℃８５％RHの雰囲気下で試料を７２時間放置後、ＦＡＣＥ接触角計（協和界面化学株式会社製、ＣＡ－Ｘ型）を用いて、機能性易接着層表面の滴下１分後における蒸留水との接触角を測定した。なお、各試料につき５回測定を行い、測定値の最大値、最小値を除いた３つの測定値の平均値を接触角とした。 (7) Water contact angle after 72 hours at 85°C and 85% RH After leaving the sample in an atmosphere of 85°C and 85% RH for 72 hours in a constant temperature and humidity chamber, water contact angle was measured using a FACE contact angle meter (manufactured by Kyowa Kaimen Kagaku Co., Ltd., CA-X). The contact angle of the surface of the functional adhesion layer with distilled water 1 minute after dropping was measured using a mold). Note that each sample was measured five times, and the average value of the three measured values excluding the maximum and minimum measured values was taken as the contact angle.
（８）８５℃８５％RH７２時間後のジヨードメタン接触角
　恒温恒湿機で８５℃８５％RHの雰囲気下で試料を７２時間放置後、ＦＡＣＥ接触角計（協和界面化学株式会社製、ＣＡ－Ｘ型）を用いて、機能性易接着層表面の滴下１分後におけるジヨードメタンとの接触角を測定した。なお、各試料につき５回測定を行い、測定値の最大値、最小値を除いた３つの測定値の平均値を接触角とした。 (8) Contact angle of diiodomethane after 72 hours at 85°C and 85%RH After leaving the sample in an atmosphere of 85°C and 85%RH for 72 hours in a constant temperature and humidity chamber, the contact angle of diiodomethane was measured using a FACE contact angle meter (manufactured by Kyowa Kaimen Kagaku Co., Ltd., CA-X). Using a mold), the contact angle with diiodomethane on the surface of the functional adhesive layer 1 minute after dropping was measured. Note that each sample was measured five times, and the average value of the three measured values excluding the maximum and minimum measured values was taken as the contact angle.
（９）ポリジメチルシロキサン含有量の測定
　ＣＤＣｌ３(重クロロホルム)／ＨＦＩＰ－ｄ(重ヘキサフルオロイソプロパノール)(1/1容量比) ０．１ｍｌに溶解後、ＴＣＥ(テトラクロロエタン)-dを ０．５ｍｌ加え１３０℃で溶解した。その溶液を１２０℃でＨ－ＮＭＲ測定を実施し、得られた成分の積分値の比率からポリジメチルシロキサンの質量比率を算出した。ポリジメチルシロキサンのピークはＮＭＲスペクトルの０．２ｐｐｍ付近に検出されたピークを使用した。空洞含有層Ａ中のポリジメチルシロキサンの含有量は層比率を用いて算出した。シリコーン樹脂は架橋されており不溶成分が多いため、添加量の定量が困難であるが、上記方法を用いればシリコーン樹脂中の可溶分のポリジメチルシロキサンは定量することができる。シリコーン樹脂添加量とポリジメチルシロキサン含有量が相関することを確認できている。 (9) Measurement of polydimethylsiloxane content After dissolving in 0.1 ml of CDCl3 (deuterated chloroform)/HFIP-d (deuterated hexafluoroisopropanol) (1/1 volume ratio), add 0.5 ml of TCE (tetrachloroethane)-d. It was added and dissolved at 130°C. The solution was subjected to H-NMR measurement at 120° C., and the mass ratio of polydimethylsiloxane was calculated from the ratio of the obtained integral values of the components. As the peak of polydimethylsiloxane, a peak detected around 0.2 ppm in the NMR spectrum was used. The content of polydimethylsiloxane in the cavity-containing layer A was calculated using the layer ratio. Since the silicone resin is crosslinked and contains many insoluble components, it is difficult to quantify the amount added, but by using the above method, the soluble polydimethylsiloxane content in the silicone resin can be determined. It has been confirmed that there is a correlation between the amount of silicone resin added and the polydimethylsiloxane content.
（１０）ポリプロピレン樹脂含有量とポリジメチルシロキサン含有量の質量比測定
　上記内容と同様にＨ－ＮＭＲ測定を実施し、得られたＮＭＲスペクトル中のポリプロピレン樹脂とポリジメチルシロキサンのピークの積分値の比率からの質量比率を算出した。 (10) Mass ratio measurement of polypropylene resin content and polydimethylsiloxane content Perform H-NMR measurement in the same manner as above, and the ratio of the integral values of the peaks of polypropylene resin and polydimethylsiloxane in the obtained NMR spectrum. The mass ratio was calculated from .
（１１）ＵＶインキとの密着性
　空洞含有ポリエステル系易接着フィルムの機能性易接着層上に、ＵＶインキ［Ｔ＆Ｋ ＴＯＫＡ(株)製、商品名「ＢＥＳＴ ＣＵＲＥ（登録商標） ＵＶ１６１藍Ｓ」］を用いて、印刷機［(株)明製作所製、商品名「ＲＩテスター」］にて印刷を施し、次いで、インキ層を塗布したフィルムに高圧水銀灯を用いて４０ｍＪ／ｃｍ２の紫外線を照射し、紫外線硬化型インキを硬化させた。次いで、ニチバン製セロハン粘着テープ（CT405AP-24）を用い、幅２４ｍｍ、長さ５０ｍｍを切り出し、インキ層表面に空気が混入しないようハンディゴムローラーで完全に付着させる。その後、垂直にセロハン粘着テープを引き剥がして、２４ｍｍ×５０ｍｍの領域において、印刷層の残存した面積を観察し、下記の基準で判断した。
　○：印刷層の残存面積が全体の９９％以上
　△：印刷層の残存面積が全体の９０％以上、９９％未満
　×：印刷層の残存面積が全体の９０％未満
　本発明においては９０％以上を合格とした。 (11) Adhesion with UV ink UV ink [manufactured by T&K TOKA Co., Ltd., product name "BEST CURE (registered trademark) UV161 Indigo S"] is applied on the functional easy-adhesion layer of the hollow-containing polyester-based easy-adhesion film. Then, the film coated with the ink layer was irradiated with 40 mJ/cm 2 of ultraviolet rays using a high-pressure mercury lamp. The UV-curable ink was cured. Next, using Nichiban's cellophane adhesive tape (CT405AP-24), cut out a piece with a width of 24 mm and a length of 50 mm, and completely adhere it with a handy rubber roller to prevent air from entering the ink layer surface. Thereafter, the cellophane adhesive tape was peeled off vertically, and the remaining area of the printed layer was observed in an area of 24 mm x 50 mm, and judged according to the following criteria.
○: The remaining area of the printed layer is 99% or more of the whole. △: The remaining area of the printed layer is 90% or more of the whole, but less than 99%. ×: The remaining area of the printed layer is less than 90% of the whole. In the present invention, the remaining area is 90% or more. was passed.
（１２）帯電防止性（表面固有抵抗値）
　空洞含有ポリエステル系易接着フィルムを５．００ｃｍ四方の正方形に３枚切り出して試料とした。表面固有抵抗値を表面抵抗測定器（日東精工アナリック製ハイレスタＭＣＰ－ＨＴ８００）を使用し、印加電圧５００Ｖ、２３℃・６５％湿度下でＪＩＳ　Ｋ６９１１準拠にて各3枚ずつ測定し平均値とした。 (12) Antistatic property (surface specific resistance value)
Three 5.00 cm square pieces of the hollow polyester easily adhesive film were cut out to serve as samples. The surface specific resistance value was measured using a surface resistance measuring device (Hiresta MCP-HT800 manufactured by Nitto Seiko Anaric) at an applied voltage of 500 V, 23°C and 65% humidity in accordance with JIS K6911, and the average value was taken as the average value. .
（１３）外観ハジキ判定
　空洞含有ポリエステル系易接着フィルム製膜の長手方向（縦方向もしくは機械方向ともいう）３００ｍｍ×幅方向２１０ｍｍの長方形フィルムを任意に１０枚切り出し、機能性易接着層を３波長ＬＥＤ灯下で目視観察によりピンホール状ハジキ個数を数えて１ｍ２当たりに換算し評価した。
　　〇：フィルム１ｍ２あたりピンホール状ハジキ個数が０個以上５個以下
　　△：フィルム１ｍ２あたりピンホール状ハジキ個数が６個以上１０個以下
　　×：フィルム１ｍ２あたりピンホール状ハジキ個数が１０個を超える
　本発明においては、５個以下を合格とした。 (13) Appearance repellency judgment Ten rectangular films measuring 300 mm in the longitudinal direction (also referred to as longitudinal direction or machine direction) x 210 mm in the width direction of the hollow-containing polyester easy-adhesive film are arbitrarily cut out, and a functional easy-adhesive layer of 3 wavelengths is cut out. The number of pinhole-shaped repellents was counted by visual observation under an LED light and evaluated by converting the number to 1 m 2 .
〇: The number of pinhole - like repellents is 0 to 5 per 1m2 of film. △: The number of pinhole-like repellents is 6 to 10 per 1m2 of film. ×: The number of pinhole - like repellents is 10 per 1m2 of film. In the present invention, 5 or less were considered to be passed.
（実施例１）
［酸化チタンマスターペレット（Ｍ１）の製造］
　極限粘度０．６２のポリエチレンテレフタレート樹脂５０質量％に平均粒子径０．３μｍ（電顕法）のアナターゼ型二酸化チタンを５０質量％混合した。そして、その混合物をベント式２軸押出機に供給し、混練りして酸化チタン含有マスターペレット（Ｍ１）を製造した。 (Example 1)
[Manufacture of titanium oxide master pellets (M1)]
50% by mass of anatase titanium dioxide having an average particle diameter of 0.3 μm (electron microscopy) was mixed with 50% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.62. The mixture was then supplied to a vented twin-screw extruder and kneaded to produce titanium oxide-containing master pellets (M1).
［シリコーン樹脂Ｓの製造］
　熱硬化型シリコーン樹脂（信越化学社製、ＫＳ―７７４）を溶剤希釈し、前記シリコーン樹脂１００質量部に対し、触媒（信越化学社製、ＣＡＴ－ＰＬ－３）を３質量部添加し、１５０℃６０秒加熱した。その加熱後、硬化したシリコーン樹脂をパウダー状にし、シリコーン樹脂Ｓを得た。 [Manufacture of silicone resin S]
Thermosetting silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KS-774) was diluted with a solvent, and 3 parts by mass of a catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-3) was added to 100 parts by mass of the silicone resin, and 150 It was heated at ℃ for 60 seconds. After heating, the cured silicone resin was powdered to obtain silicone resin S.
［未延伸フィルムの製造］
　極限粘度０．６２のポリエチレンテレフタレート樹脂９３質量％、およびＭＦＲ＝２．５、Ｍｗ＝３２００００、Ｍｗ／Ｍｎ＝４．０、荷重たわみ温度＝９２℃のポリプロピレン樹脂６．９２質量％、シリコーン樹脂Ｓ８００ｐｐｍを混合した。そして、その混合物を真空乾燥を施し、空洞含有層Ａの原料とした。一方、前記酸化チタン含有マスターペレット（Ｍ１）３０質量％と極限粘度０．６２のポリエチレンテレフタレート樹脂７０質量％とをペレット混合した。そして、その混合物を真空乾燥を施し、第１被覆層Ｂ１及び第２被覆層Ｂ２の原料とした。これらの原料を別々の押出機に供給し、２８５℃で溶融し、空洞含有層Ａ、第１被覆層Ｂ１及び第２被覆層Ｂ２がＢ１／Ａ／Ｂ２の順になるよう積層した。その積層体を、厚み比率が１０／８０／１０となるようにフィードブロックで接合した。その接合体を、Ｔダイから３０℃に調節された冷却ドラム上に押し出し、２種３層構成の未延伸フィルムを製造した。 [Manufacture of unstretched film]
93% by mass of polyethylene terephthalate resin with intrinsic viscosity 0.62, 6.92% by mass of polypropylene resin with MFR = 2.5, Mw = 320000, Mw/Mn = 4.0, deflection temperature under load = 92°C, silicone resin S 800ppm were mixed. Then, the mixture was vacuum dried and used as a raw material for the cavity-containing layer A. On the other hand, 30% by mass of the titanium oxide-containing master pellets (M1) and 70% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.62 were mixed into pellets. Then, the mixture was vacuum dried and used as a raw material for the first coating layer B1 and the second coating layer B2. These raw materials were supplied to separate extruders, melted at 285° C., and laminated so that the cavity-containing layer A, the first coating layer B1, and the second coating layer B2 were in the order of B1/A/B2. The laminates were joined using a feed block so that the thickness ratio was 10/80/10. The bonded body was extruded from a T-die onto a cooling drum adjusted to 30° C. to produce an unstretched film having two types and three layers.
［機能性易接着層］
（カチオン系帯電防止剤Ａ）
　Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン１１６ｇと炭素数１７のステアリン酸２８５ｇを用いて１００℃ 、窒素雰囲気下で１０時間エステル化反応を行い、４級化溶媒としてテトラヒドロフランを加え、対象アミンにジメチル硫酸を規定量投入し、７０℃、１０時間程度反応させた。反応後、減圧で溶媒を留去した後、イソプロパノールを加えて、所望の固形分濃度に調節して、４級アンモニウムエトサルフェート塩を有するカチオン系帯電防止剤Ａのイソプロパノール溶液を得た。 [Functional adhesive layer]
(Cationic antistatic agent A)
An esterification reaction was carried out using 116 g of N,N-dimethyl-1,3-propanediamine and 285 g of stearic acid having 17 carbon atoms at 100°C in 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. After the reaction, the solvent was distilled off under reduced pressure, and then isopropanol was added to adjust the solid content to a desired concentration to obtain an isopropanol solution of cationic antistatic agent A having a quaternary ammonium ethosulfate salt.
（ポリカーボネート構造を有するウレタン樹脂Ｂの重合）
　機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた４つ口フラスコに、４，４－ジシクロヘキシルメタンジイソシアネート２２質量部、数平均分子量７００のポリエチレングリコールモノメチルエーテル２０質量部、数平均分子量２１００のポリヘキサメチレンカーボネートジオール５３質量部、ネオペンチルグリコール５質量部、及び溶剤としてアセトン８４．００質量部を投入し、窒素雰囲気下、７５℃において３時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、ヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物（旭化成ケミカルズ製、デュラネート（登録商標）ＴＰＡ、３官能）１６質量部を投入し、窒素雰囲気下、７５℃において１時間撹拌し、反応液が所定のアミン当量に達したことを確認した。その後、反応液温度を５０℃に下げ、メチルエチルケトオキシム７質量部を滴下した。この反応液を４０℃にまで降温した後、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水４５０ｇを添加して、２５℃に調整して、２０００ｍｉｎ－１で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、水分散性ウレタン樹脂Ｂの固形分３５質量％の溶液を調製した。 (Polymerization of urethane resin B having polycarbonate structure)
In a four-neck flask equipped with a vacuum cleaner, a Dimroth condenser, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 22 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 20 parts by mass of polyethylene glycol monomethyl ether with a number average molecular weight of 700, 53 parts by mass of polyhexamethylene carbonate diol having a number average molecular weight of 2100, 5 parts by mass of neopentyl glycol, and 84.00 parts by mass of acetone as a solvent were added, and the mixture was stirred at 75°C for 3 hours under a nitrogen atmosphere until the reaction solution reached a predetermined level. It was confirmed that the amine equivalent of . Next, 16 parts by mass of a polyisocyanate compound having an isocyanurate structure made from hexamethylene diisocyanate (manufactured by Asahi Kasei Chemicals, Duranate (registered trademark) TPA, trifunctional) was added, and the mixture was stirred for 1 hour at 75°C under a nitrogen atmosphere. It was confirmed that the reaction solution had reached a predetermined amine equivalent. Thereafter, the temperature of the reaction solution was lowered to 50° C., and 7 parts by mass of methyl ethyl ketoxime was added dropwise. After cooling this reaction solution to 40° C., a polyurethane prepolymer solution was obtained. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, the temperature was adjusted to 25°C, and while stirring and mixing at 2000 min -1 , a polyurethane prepolymer solution was added and water-dispersed. . Thereafter, acetone and part of the water were removed under reduced pressure to prepare a solution of water-dispersible urethane resin B with a solid content of 35% by mass.
（ブロックイソシアネート架橋剤Ｃの重合）
　攪拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物（旭化成ケミカルズ製、デュラネート（登録商標）ＴＰＡ）１００質量部、プロピレングリコールモノメチルエーテルアセテート５５質量部、ポリエチレングリコールモノメチルエーテル（平均分子量７５０）３０質量部を仕込み、窒素雰囲気下、７０℃で４時間保持した。その後、反応液温度を５０℃に下げ、メチルエチルケトオキシム４７質量部を滴下した。反応液の赤外スペクトルを測定し、イソシアネート基の吸収が消失したことを確認し、水２１０質量部を加えオキシムブロックイソシアネート架橋剤（Ｃ）の固形分４０質量％の水分散液を得た。当該ブロックイソシアネート架橋剤の官能基数は３、ＮＣＯ当量は１７０である。 (Polymerization of block isocyanate crosslinking agent C)
In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 100 parts by mass of a polyisocyanate compound having an isocyanurate structure made from hexamethylene diisocyanate (manufactured by Asahi Kasei Chemicals, Duranate (registered trademark) TPA), and 55 parts by mass of propylene glycol monomethyl ether acetate. 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 750) were charged, and the mixture was maintained at 70° C. for 4 hours under a nitrogen atmosphere. Thereafter, the temperature of the reaction solution was lowered to 50° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise. The infrared spectrum of the reaction solution was measured to confirm that the absorption of isocyanate groups had disappeared, and 210 parts by mass of water was added to obtain an aqueous dispersion of oxime block isocyanate crosslinking agent (C) with a solid content of 40% by mass. The number of functional groups of the blocked isocyanate crosslinking agent is 3, and the NCO equivalent is 170.
（共重合ポリエステル樹脂Ｄ－１の重合）
　攪拌機、温度計、および部分還流式冷却器を具備するステンレススチール製オートクレーブに、ジメチルテレフタレート１９４．２質量部、ジメチルイソフタレート１８４．５質量部、ジメチル－５－ナトリウムスルホイソフタレート１４．８質量部、ネオペンチルグリコール１８５質量部、エチレングリコール１８８質量部、およびテトラ－ｎ－ブチルチタネート０．２質量部を仕込み、１６０℃から２２０℃の温度で４時間かけてエステル交換反応を行なった。次いで２５５℃まで昇温し、反応系を徐々に減圧した後、３０Ｐａの減圧下で１時間３０分反応させ、共重合ポリエステル樹脂（Ｄ－１）を得た。得られた共重合ポリエステル樹脂（Ｄ－１）は、淡黄色透明であった。共重合ポリエステル樹脂（Ｄ－１）の還元粘度を測定したところ，０．４０ｄｌ／ｇであった。ＤＳＣによるガラス転移温度は６５℃であった。 (Polymerization of copolymerized polyester resin D-1)
In a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial reflux condenser, 194.2 parts by weight of dimethyl terephthalate, 184.5 parts by weight of dimethyl isophthalate, and 14.8 parts by weight of dimethyl-5-sodium sulfoisophthalate were added. , 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 a transesterification reaction was carried out at a temperature of 160° C. to 220° C. over 4 hours. Next, the temperature was raised to 255° C., the pressure of the reaction system was gradually reduced, and the reaction was carried out for 1 hour and 30 minutes under a reduced pressure of 30 Pa to obtain a copolymerized polyester resin (D-1). The obtained copolymerized polyester resin (D-1) was pale yellow and transparent. The reduced viscosity of the copolymerized polyester resin (D-1) was measured and found to be 0.40 dl/g. The glass transition temperature by DSC was 65°C.
（ポリエステル水分散体Ｄｗ－１の調製）
　攪拌機、温度計と還流装置を備えた反応器に、共重合ポリエステル樹脂（Ｄ－１）２５質量部、エチレングリコールモノ－ｎ－ブチルエーテル１０質量部を入れ、１１０℃で加熱、攪拌し樹脂を溶解した。樹脂が完全に溶解した後、水６５質量部をポリエステル溶液に攪拌しつつ徐々に添加した。添加後、液を攪拌しつつ室温まで冷却して、固形分２５質量％の乳白色のポリエステル水分散体（Ｄｗ－１）を作製した。 (Preparation of polyester water dispersion Dw-1)
Into a reactor equipped with a stirrer, a thermometer, and a reflux device, put 25 parts by mass of copolymerized polyester resin (D-1) and 10 parts by mass of ethylene glycol mono-n-butyl ether, and heat and stir at 110°C to dissolve the resin. did. After the resin was completely dissolved, 65 parts by mass of water was gradually added to the polyester solution while stirring. After the addition, the liquid was cooled to room temperature while stirring to produce a milky white polyester aqueous dispersion (Dw-1) with a solid content of 25% by mass.
（実施例１）
　機能性易接着層を構成する塗布化合物の塗布液中の固形分は以下のとおりである。
　機能性易接着層に含まれる固形分の総和を１００質量％とする。
　・カチオン系帯電防止剤Ａ：６．２質量％
　・ポリカーボネート構造を有するウレタン樹脂Ｂ：２２．８質量％
　・ブロックイソシアネート架橋剤Ｃ：１０．９質量％
　・ポリエステル樹脂Ｄｗ－１：５４．６質量％
　・シリコーン系界面活性剤：０．４質量％
　・ｐＨ調整剤（炭酸水素ナトリウム）：２．４質量％
　ウレタン樹脂（Ｂ）／架橋剤（Ｃ）／ポリエステル樹脂（Ｄｗ－１）の固形分質量比が２８／１２／６０である。 (Example 1)
The solid content in the coating liquid of the coating compound constituting the functional adhesive layer is as follows.
The total solid content contained in the functional adhesive layer is 100% by mass.
・Cationic antistatic agent A: 6.2% by mass
・Urethane resin B with polycarbonate structure: 22.8% by mass
・Blocked isocyanate crosslinking agent C: 10.9% by mass
・Polyester resin Dw-1: 54.6% by mass
・Silicone surfactant: 0.4% by mass
・pH adjuster (sodium hydrogen carbonate): 2.4% by mass
The solid content mass ratio of urethane resin (B)/crosslinking agent (C)/polyester resin (Dw-1) is 28/12/60.
［空洞含有ポリエステル系易接着フィルム作製］
　次のような製膜条件で空洞含有ポリエステル系易接着フィルムを作製した。すなわち、得られた未延伸フィルムを、加熱ロールを用いて７０℃に均一加熱し、周速が異なる２対のニップロール間で３．４倍に縦延伸した。このとき、未延伸フィルムの補助加熱装置として、ニップロール中間部に金反射膜を備えた赤外線加熱ヒータ（定格２０Ｗ／ｃｍ）をフィルムの両面に対向して設置（フィルム表面から１ｃｍの距離）、加熱した。このようにして得られた１軸延伸フィルムの片面に、前記の塗布構成を用い、リバースグラビアコート法によりＷＥＴ塗工量が７ｇ／ｍ２になるように塗布した後テンターに導き、１４０℃に加熱して４．０倍に横延伸し、幅固定して、２３５℃で熱処理を施し、更に２１０℃で幅方向に３％緩和させることにより、フィルム厚み５０μｍ、機能性易接着層厚み０．１１ｇ／ｍ２の空洞含有ポリエステル系易接着フィルムを得た。見かけ密度、水接触角、ジヨードメタン接触角、色調ｂ値、全光線透過率および製膜性の結果を表１に示した。なお、機能性易接着層表面の６０度正反射におけるグロス値は７０％であり、光沢感に優れた機能性易接着層であった。 [Production of hollow-containing polyester-based easily adhesive film]
A cavity-containing polyester-based easily adhesive film was produced under the following film-forming conditions. That is, the obtained unstretched film was uniformly heated to 70° C. using a heating roll, and longitudinally stretched 3.4 times between two pairs of nip rolls having different circumferential speeds. At this time, as an auxiliary heating device for the unstretched film, an infrared heater (rated at 20 W/cm) equipped with a gold reflective film in the middle of the nip roll was installed facing both sides of the film (at a distance of 1 cm from the film surface), and heated. did. One side of the uniaxially stretched film thus obtained was coated using the above-mentioned coating configuration using the reverse gravure coating method so that the wet coating amount was 7 g/m 2 , and then introduced into a tenter and heated to 140°C. By heating and transversely stretching 4.0 times, fixing the width, heat-treating at 235°C, and further relaxing 3% in the width direction at 210°C, a film with a thickness of 50 μm and a functional adhesive layer with a thickness of 0. A cavity-containing polyester easily adhesive film having a weight of 11 g/m 2 was obtained. Table 1 shows the results of apparent density, water contact angle, diiodomethane contact angle, color b value, total light transmittance, and film formability. The gloss value of the surface of the functional adhesive layer in 60 degree specular reflection was 70%, indicating that the functional adhesive layer had excellent gloss.
（実施例２、３、５）
　実施例１において、空洞含有層Ａの原料比率を表１のように変更した以外は実施例１と同様の方法で空洞含有ポリエステル系易接着フィルムを得た。 (Examples 2, 3, 5)
In Example 1, a cavity-containing polyester-based easily adhesive film was obtained in the same manner as in Example 1, except that the raw material ratio of the cavity-containing layer A was changed as shown in Table 1.
（実施例４）
　実施例１において、空洞含有層Ａの原料比率と層比率を表１のように変更し、機能性易接着層の塗布組成を以下に変更した以外は実施例１と同様の方法で空洞含有ポリエステル系易接着フィルムを得た。
  機能性易接着層を構成する化合物の塗布液中の固形分は以下のとおりである。
  機能性易接着層に含まれる固形分の総和を１００質量％とする。
　・コロイダルシリカ粒子（Ｅ）（平均粒子径：４５０ｎｍ）：４８．８質量％
　・カチオン系帯電防止剤Ａ：２．１質量％
　・ポリカーボネート構造を有するウレタン樹脂Ｂ：１２．２質量％
　・ブロックイソシアネート架橋剤Ｃ：１２．２質量％
　・ポリエステル樹脂Ｄｗ－１：２４．４質量％
　・シリコーン系界面活性剤：０．１質量％
　・ｐＨ調整剤（炭酸水素ナトリウム）：０．２質量％
　ウレタン樹脂（Ｂ）／架橋剤（Ｃ）／ポリエステル樹脂（Ｄｗ－１）の質量比が２５／２５／５０／である。
　上記機能性易接着層の構成とし、ＷＥＴ塗工量を１０ｇ／ｍ２に変更した以外は実施例１と同様に、乾燥後の機能性機能性易接着層厚み０．５５ｇ／ｍ２の空洞含有ポリエステル系易接着フィルムを得た。なお機能性易接着層表面の６０度正反射におけるグロス値は９．０％であり、マット感に優れた機能性易接着層を得た。 (Example 4)
In Example 1, the cavity-containing polyester was prepared in the same manner as in Example 1, except that the raw material ratio and layer ratio of the cavity-containing layer A were changed as shown in Table 1, and the coating composition of the functional adhesive layer was changed as follows. An easily adhesive film was obtained.
The solid content in the coating liquid of the compound constituting the functional adhesive layer is as follows.
The total solid content contained in the functional adhesive layer is 100% by mass.
- Colloidal silica particles (E) (average particle diameter: 450 nm): 48.8% by mass
・Cationic antistatic agent A: 2.1% by mass
・Urethane resin B with polycarbonate structure: 12.2% by mass
・Blocked isocyanate crosslinking agent C: 12.2% by mass
・Polyester resin Dw-1: 24.4% by mass
・Silicone surfactant: 0.1% by mass
・pH adjuster (sodium hydrogen carbonate): 0.2% by mass
The mass ratio of urethane resin (B)/crosslinking agent (C)/polyester resin (Dw-1) is 25/25/50/.
The structure of the functional easy-adhesive layer was the same as in Example 1 except that the wet coating amount was changed to 10 g/m 2 , except that the functional easy-adhesive layer had a thickness of 0.55 g/m 2 after drying. A polyester containing easily adhesive film was obtained. The gloss value of the surface of the functional adhesive layer in 60 degree specular reflection was 9.0%, and a functional adhesive layer with excellent matte feel was obtained.
（比較例１）
　実施例１において、空洞含有層Ａのシリコーン樹脂を０ｐｐｍ、ポリエチレンテレフタレート樹脂を９３．０８質量％に変更及び機能性易接着層を設けない以外は実施例１と同様の方法で空洞含有ポリエステル系フィルムを得た。比較例１の空洞含有ポリエステル系フィルムでは、見かけ密度が１．２０ｇ／ｃｍ３を超えるため、軽量性やクッション性が悪かった。質量が大きいことから製造コストも高くなる。また、比較例１の空洞含有ポリエステル系フィルムは、全光線透過率も高く、実施例１～５に比べて隠蔽性も悪く、機能性易接着層が無いことでＵＶインキ密着性に乏しく、帯電防止性も発現せず静電気によりフィルム同士が吸着するなど取扱い性に苦慮するものであった。 (Comparative example 1)
In Example 1, a cavity-containing polyester film was prepared in the same manner as in Example 1, except that the silicone resin in the cavity-containing layer A was changed to 0 ppm, the polyethylene terephthalate resin was changed to 93.08% by mass, and the functional adhesive layer was not provided. I got it. The cavity-containing polyester film of Comparative Example 1 had an apparent density of more than 1.20 g/cm 3 and therefore had poor lightness and cushioning properties. Since the mass is large, the manufacturing cost is also high. In addition, the cavity-containing polyester film of Comparative Example 1 has a high total light transmittance, has poor hiding properties compared to Examples 1 to 5, has poor UV ink adhesion due to the lack of a functional adhesive layer, and has no electrostatic charge. The film did not exhibit any preventive properties, and the films attracted each other due to static electricity, making it difficult to handle.
（比較例２）
　実施例１において、前述の層比率を０％にした以外は実施例１と同様の方法で空洞含有ポリエステル系易接着フィルムを得た。全光線透過率がやや高く、実施例１～５に比べて隠蔽性が悪かった。また色調ｂ値が大きく、実施例１～５に比べて白色度がやや低く、黄色味が強かった。また、比較例２の空洞含有ポリエステル系易接着フィルムは、シリコーン樹脂の影響により、得られた機能性易接着層の外観はピンホールハジキの欠点が見られた。また機能性易接着層に塗布したＵＶインキも同様にピンホールハジキの欠点抜けが発生し、密着性も劣る結果であった。。比較例２は、作製した空洞含有ポリエステル系易接着フィルムに対する加工工程でのコーティング抜けや次工程における印刷抜けを抑制することができない。 (Comparative example 2)
In Example 1, a cavity-containing polyester-based easily adhesive film was obtained in the same manner as in Example 1, except that the layer ratio was changed to 0%. The total light transmittance was slightly high, and the hiding power was poor compared to Examples 1 to 5. In addition, the color tone b value was large, the whiteness was slightly lower than Examples 1 to 5, and the yellowish tinge was strong. In addition, in the cavity-containing polyester-based easy-adhesive film of Comparative Example 2, the appearance of the obtained functional easy-adhesive layer showed defects such as pinhole repellency due to the influence of the silicone resin. In addition, the UV ink applied to the functional adhesive layer also showed pinhole repellency and poor adhesion. . In Comparative Example 2, it is not possible to suppress coating omission in the processing step of the produced hollow-containing polyester-based easily adhesive film and printing omission in the next step.
（比較例３）
　実施例１において、空洞含有層Ａの原料比率を表１のように変更した以外は実施例１と同様の方法で空洞含有ポリエステル系易接着フィルムを得た。比較例３の空洞含有ポリエステル系易接着フィルムでは、見かけ密度が０．８０ｇ／ｃｍ３より低いことから、フィルム自体の腰感が弱く、表面強度も低下する結果であった。比較例３の製膜性は、実施例１～５の製膜性に比べて悪かった。
　以上より、本発明に係る空洞含有ポリエステル系易接着フィルムは、空洞含有層Ａがシリコーン樹脂を微量含有することで例えば加工工程においてポリプロピレン樹脂の熱劣化を抑制でき空洞発現性を維持できる。そのため、本発明に係る空洞含有ポリエステル系易接着フィルムは、易接着性に優れ、見かけ密度が０．８０～１．２０であっても優れた軽量性、製膜性、隠蔽性及び白色度を有する。特に実施例１～５に係る空洞含有ポリエステル系易接着フィルムは、易接着性に優れ、見かけ密度が０．８０～１．１０であっても優れた軽量性、製膜性、隠蔽性及び白色度を有する。 (Comparative example 3)
In Example 1, a cavity-containing polyester-based easily adhesive film was obtained in the same manner as in Example 1, except that the raw material ratio of the cavity-containing layer A was changed as shown in Table 1. Since the hollow polyester easily adhesive film of Comparative Example 3 had an apparent density lower than 0.80 g/cm 3 , the film itself had a weak feeling of stiffness and its surface strength was also reduced. The film forming properties of Comparative Example 3 were worse than those of Examples 1 to 5.
As described above, in the cavity-containing polyester-based easily adhesive film according to the present invention, since the cavity-containing layer A contains a small amount of silicone resin, thermal deterioration of the polypropylene resin can be suppressed, for example, in the processing process, and cavity development can be maintained. Therefore, the cavity-containing polyester-based easy-adhesive film of the present invention has excellent easy-adhesive properties, and even with an apparent density of 0.80 to 1.20, it has excellent lightness, film-forming properties, hiding properties, and whiteness. have In particular, the cavity-containing polyester-based easy-adhesive films according to Examples 1 to 5 have excellent easy-adhesive properties, and even when the apparent density is 0.80 to 1.10, they have excellent lightness, film formability, concealment property, and white color. have a degree.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以上のように本発明の空洞含有ポリエステル系易接着フィルムは、軽量性、製膜性、隠蔽性、白色度に優れ、易接着性を有することから、例えばラベル、カード、包装材料、電子材料、偏光板や積層セラミックコンデンサ製造時等に使用する離型フィルムなどの基材用途として好適に用いられる。
  As described above, the cavity-containing polyester-based easy-adhesive film of the present invention has excellent lightness, film-forming properties, hiding properties, and whiteness, and has easy-adhesive properties, so it can be used, for example, in labels, cards, packaging materials, electronic materials, etc. It is suitably used as a base material for polarizing plates and release films used in the manufacture of multilayer ceramic capacitors.

Claims (11)

  1. 　無機顔料を含有するポリエステル樹脂を含む第１被覆層Ｂ１と、内部に空洞を含有する空洞含有層Ａと、無機顔料を含有するポリエステル樹脂を含む第２被覆層Ｂ２と、がこの順序に積層され、前記第１被覆層Ｂ１上に機能性易接着層を有し、
    　見かけ密度が０．８０ｇ／ｃｍ３以上１．２０ｇ／ｃｍ３以下であり、
    　前記空洞含有層Ａが、ポリエステル樹脂とポリプロピレン樹脂とシリコーン樹脂を含有する組成物を含む空洞含有ポリエステル系易接着フィルム。     A first coating layer B1 containing a polyester resin containing an inorganic pigment, a cavity-containing layer A containing cavities therein, and a second coating layer B2 containing a polyester resin containing an inorganic pigment are laminated in this order. , having a functional adhesive layer on the first coating layer B1,
    The apparent density is 0.80 g/cm 3 or more and 1.20 g/cm 3 or less,
    A cavity-containing polyester-based easily adhesive film in which the cavity-containing layer A includes a composition containing a polyester resin, a polypropylene resin, and a silicone resin.
  2. 　前記空洞含有層Ａにおいて、シリコーン樹脂中のポリジメチルシロキサンの含有量が、空洞含有層Ａの全質量に対して１ｐｐｍ以上２５００ｐｐｍ以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The cavity-containing polyester easily adhesive film according to claim 1, wherein in the cavity-containing layer A, the content of polydimethylsiloxane in the silicone resin is 1 ppm or more and 2,500 ppm or less based on the total mass of the cavity-containing layer A.
  3. 　前記空洞含有層Ａにおいて、シリコーン樹脂中のポリジメチルシロキサンの含有量が、ポリプロピレン樹脂１００質量％に対して０．００５質量％以上２．０００質量％以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The cavity-containing polyester according to claim 1, wherein in the cavity-containing layer A, the content of polydimethylsiloxane in the silicone resin is 0.005% by mass or more and 2.000% by mass or less based on 100% by mass of the polypropylene resin. Easy adhesive film.
  4. 　前記第１被覆層Ｂ１及び前記第２被覆層Ｂ２中の無機顔料が酸化チタンである請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The cavity-containing polyester-based easily adhesive film according to claim 1, wherein the inorganic pigment in the first coating layer B1 and the second coating layer B2 is titanium oxide.
  5. 　前記第１被覆層Ｂ１の厚み、前記空洞含有層Ａの厚み及び前記第２被覆層Ｂ２の厚みの合計に対する前記第１被覆層Ｂ１の厚み及び前記第２被覆層Ｂ２の厚みの合計の比率が、６％以上４０％以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The ratio of the sum of the thicknesses of the first coating layer B1 and the second coating layer B2 to the sum of the thickness of the first coating layer B1, the thickness of the cavity-containing layer A, and the thickness of the second coating layer B2 is 2. The cavity-containing polyester easily adhesive film according to claim 1, wherein the cavity content is 6% or more and 40% or less.
  6. 　全光線透過率が１％以上３０％以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The cavity-containing polyester easily adhesive film according to claim 1, which has a total light transmittance of 1% or more and 30% or less.
  7. 　見かけ密度が０．８０ｇ／ｃｍ３以上１．１０ｇ／ｃｍ３以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The cavity-containing polyester easily adhesive film according to claim 1, which has an apparent density of 0.80 g/cm 3 or more and 1.10 g/cm 3 or less.
  8. 　前記機能性易接着層の、以下の評価方法による密着残存面積が９９％以上である請求項１に記載の空洞含有ポリエステル系易接着フィルム。
    （但し、密着残存面積は、以下の評価方法による。
    　空洞含有ポリエステル系易接着フィルムの機能性易接着層上に、ＵＶインキ［Ｔ＆Ｋ ＴＯＫＡ(株)製、商品名「ＢＥＳＴ ＣＵＲＥ（登録商標） ＵＶ１６１藍Ｓ」］を用いて、印刷機［(株)明製作所製、商品名「ＲＩテスター」］にて印刷を施し、次いで、インキ層を塗布したフィルムに高圧水銀灯を用いて４０ｍＪ／ｃｍ２の紫外線を照射し、紫外線硬化型インキを硬化させる。次いで、ニチバン製セロハン粘着テープ（CT405AP-24）を用い、幅２４ｍｍ、長さ５０ｍｍを切り出し、インキ層表面に空気が混入しないようハンディゴムローラーで完全に付着させる。その後、垂直にセロハン粘着テープを引き剥がして、２４ｍｍ×５０ｍｍの領域において、印刷層の残存した面積（密着残存面積）（％）を観察し求める。）     The cavity-containing polyester easily adhesive film according to claim 1, wherein the functional adhesive layer has a remaining adhesion area of 99% or more according to the following evaluation method.
    (However, the adhesion remaining area is based on the following evaluation method.
    On the functional easy-adhesion layer of the hollow polyester-based easy-adhesion film, UV ink [manufactured by T&K TOKA Co., Ltd., product name "BEST CURE (registered trademark) UV161 Indigo S"] was applied to a printing machine [made by T&K TOKA Co., Ltd. Printing was carried out using a product named "RI Tester" manufactured by Mei Seisakusho, and then the film coated with the ink layer was irradiated with ultraviolet rays of 40 mJ/cm 2 using a high-pressure mercury lamp to cure the ultraviolet curable ink. Next, using Nichiban's cellophane adhesive tape (CT405AP-24), cut out a piece with a width of 24 mm and a length of 50 mm, and completely adhere it with a handy rubber roller to prevent air from entering the ink layer surface. Thereafter, the cellophane adhesive tape is peeled off vertically, and the remaining area of the printed layer (remaining adhesion area) (%) is observed and determined in an area of 24 mm x 50 mm. )
  9. 　前記機能性易接着層が帯電防止剤を含有しており、表面固有抵抗値が１．０×１０１３Ω／ｓｑ以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。 The cavity-containing polyester-based easy-adhesive film according to claim 1, wherein the functional easily-adhesive layer contains an antistatic agent and has a surface resistivity of 1.0×10 13 Ω/sq or less.
  10. 　前記機能性易接着層のピンホール状ハジキ個数が５個／ｍ２以下である請求項１に記載の空洞含有ポリエステル系易接着フィルム。
    （但し、機能性易接着層のピンホール状ハジキ個数は、空洞含有ポリエステル系易接着フィルムの機能性易接着層を３波長蛍光灯下で目視観察によりピンホール状ハジキ個数を数えて評価する。）     The cavity-containing polyester-based easily adhesive film according to claim 1, wherein the number of pinhole-like repellents in the functional easily adhesive layer is 5 pieces/m 2 or less.
    (However, the number of pinhole repellents in the functional adhesive layer is evaluated by visually observing the functional adhesive layer of the hollow polyester adhesive film under a three-wavelength fluorescent lamp and counting the number of pinhole repellents. )
  11. 　ラベル、カード、包装材料、又は離型フィルムの用途に用いられる請求項１から１０のいずれか１項に記載の空洞含有ポリエステル系易接着フィルム。
          The cavity-containing polyester easily adhesive film according to any one of claims 1 to 10, which is used for labels, cards, packaging materials, or release films.
PCT/JP2023/024899 2022-08-22 2023-07-05 Void-containing polyester-based easy adhesion film WO2024042879A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026089A (en) * 1999-05-12 2001-01-30 Mitsubishi Polyester Film Copp Polyester film containing fine bubble
WO2022059580A1 (en) * 2020-09-15 2022-03-24 東洋紡株式会社 Cavity-containing polyester film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026089A (en) * 1999-05-12 2001-01-30 Mitsubishi Polyester Film Copp Polyester film containing fine bubble
WO2022059580A1 (en) * 2020-09-15 2022-03-24 東洋紡株式会社 Cavity-containing polyester film

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