WO2024042879A1 - Film d'adhérence facile à base de polyester contenant des vides - Google Patents

Film d'adhérence facile à base de polyester contenant des vides 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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Prior art keywords
cavity
layer
polyester
resin
adhesive film
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PCT/JP2023/024899
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English (en)
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/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Le film d'adhérence facile à base de polyester contenant des vides selon la présente invention : possède une première couche de revêtement B1 qui contient une résine de polyester contenant un pigment inorganique, une couche contenant des vides A qui contient des vides à l'intérieur de celle-ci, et une seconde couche de revêtement B2 qui contient une résine de polyester contenant un pigment inorganique, stratifiées dans cet ordre ; possède une couche d'adhérence facile fonctionnelle sur la première couche de revêtement B1 ; et a une densité apparente de 0,80 g/cm3 ou plus et de 1,20 g/cm3 ou moins, la couche contenant des vides A renfermant une composition qui contient une résine de polyester, une résine de polypropylène et une résine de silicone.
PCT/JP2023/024899 2022-08-22 2023-07-05 Film d'adhérence facile à base de polyester contenant des vides WO2024042879A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026089A (ja) * 1999-05-12 2001-01-30 Mitsubishi Polyester Film Copp 微細気泡含有ポリエステルフィルム
WO2022059580A1 (fr) * 2020-09-15 2022-03-24 東洋紡株式会社 Film de polyester contenant une cavité

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026089A (ja) * 1999-05-12 2001-01-30 Mitsubishi Polyester Film Copp 微細気泡含有ポリエステルフィルム
WO2022059580A1 (fr) * 2020-09-15 2022-03-24 東洋紡株式会社 Film de polyester contenant une cavité

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