WO2013011826A1 - Film thermorétractable et étiquette thermorétractable - Google Patents

Film thermorétractable et étiquette thermorétractable Download PDF

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Publication number
WO2013011826A1
WO2013011826A1 PCT/JP2012/066888 JP2012066888W WO2013011826A1 WO 2013011826 A1 WO2013011826 A1 WO 2013011826A1 JP 2012066888 W JP2012066888 W JP 2012066888W WO 2013011826 A1 WO2013011826 A1 WO 2013011826A1
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WIPO (PCT)
Prior art keywords
mass
heat
water
film
wax
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PCT/JP2012/066888
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English (en)
Japanese (ja)
Inventor
安井　義勝
土井　満
孝典 野崎
直之 丸市
歩夢 中原
圭介 中
Original Assignee
昭和電工株式会社
グンゼ株式会社
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Priority to JP2013524649A priority Critical patent/JP5519864B2/ja
Publication of WO2013011826A1 publication Critical patent/WO2013011826A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/744—Labels, badges, e.g. marker sleeves

Definitions

  • the present invention relates to a heat-shrinkable film having excellent surface wear resistance during transportation when used as a heat-shrinkable label for containers, and a heat-shrinkable label using the film.
  • the heat-shrinkable film used for PET bottle beverages and the like is composed of various film substrates using polystyrene resin, polyester resin, polyolefin resin, and the like.
  • Patent Document 1 a proposal for improving the wear resistance of the surface has been made (for example, Patent Document 1).
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a heat-shrinkable film having excellent wear resistance using an aqueous coating material having a low environmental load.
  • the present invention provides an emulsion (A) comprising a polymer of an ethylenically unsaturated monomer having a water-soluble polyester or water-dispersible polyester as a protective colloid and a wax-based lubricant. It has been found that a heat-shrinkable film characterized by applying an aqueous coating material made of (B) to a film substrate made of a polyester resin or a polystyrene resin is excellent in wear resistance. That is, the present invention provides the following heat-shrinkable film.
  • the present invention relates to an aqueous coating material comprising an emulsion (A) comprising a polymer of an ethylenically unsaturated monomer having a water-soluble polyester or water-dispersible polyester as a protective colloid and a wax-based lubricant (B).
  • A emulsion
  • B wax-based lubricant
  • the wax lubricant (B) is a polyethylene wax or a polypropylene wax, and preferably has a melting point of 90 to 160 ° C.
  • the content of the wax-based lubricant (B) is preferably 1 to 30% by mass with respect to the resin solid content of the emulsion (A).
  • the solid content of the water-soluble polyester or water-dispersible polyester is preferably 10 to 90% by mass with respect to the solid content of the emulsion (A).
  • the glass transition temperature of the polymer is preferably 0 to 60 ° C.
  • the glass transition temperature of the water-soluble polyester or water-dispersible polyester is preferably 30 to 80 ° C.
  • the present invention also relates to a heat-shrinkable label characterized by using these heat-shrinkable films.
  • the film of the present invention is excellent in abrasion resistance, and even when it is transported by being attached as a label to a container, the scratch and abrasion of the label are extremely small and the commercial value is not impaired.
  • the heat-shrinkable film of the present invention has a coating material layer (hereinafter referred to as an abrasion-resistant layer) having an abrasion resistance made of an aqueous coating material.
  • the aqueous coating material used for the heat-shrinkable film contains an emulsion (A) obtained by emulsion polymerization of an ethylenically unsaturated monomer having a water-soluble polyester or water-dispersible polyester as a protective colloid.
  • the solid content of the water-soluble polyester or water-dispersible polyester is 10 to 90% by mass in the solid content of the emulsion (A) obtained by emulsion polymerization of an ethylenically unsaturated monomer.
  • the content is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass.
  • the content of the water-soluble polyester or water-dispersible polyester is less than 10% by mass, the effect of improving the adhesion to a film substrate, particularly a polyester resin, tends to be small, and the inclusion of the water-soluble polyester or water-dispersible polyester
  • the amount exceeds 90% by mass the water resistance tends to decrease such as whitening or loss of adhesion to the heat-shrinkable film when water is attached or boiled with water.
  • the ethylenically unsaturated monomer used in the present invention may be any monomer having at least one polymerizable vinyl group, and has, for example, a linear, branched or cyclic alkyl chain (meth).
  • Typical examples include acrylic esters, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, heterocyclic vinyl compounds such as vinylpyrrolidone, hydroxyalkyl (meth) acrylates, alkylamino (meth) acrylates, vinyl acetate and vinyl alkanoates.
  • Vinyl esters monoolefins (ethylene, propylene, butylene, isobutylene, etc.), conjugated diolefins (butadiene, isoprene, chloroprene, etc.), ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids (acrylic acid, methacrylic acid, Crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.
  • Vinyl cyanide compounds such as acrylonitrile, carbonyl group-containing ethylenically unsaturated monomers acrolein and diacetone acrylamide, etc., sulfonic acid group-containing ethylenically unsaturated monomers such as p- toluenesulfonic acid.
  • styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl acrylate are preferable in consideration of the reactivity and water resistance of emulsion polymerization.
  • These ethylenically unsaturated monomers may be used alone or in combination of two or more.
  • the content of the polymer obtained by polymerizing the ethylenically unsaturated monomer is preferably 10 to 90% by mass, and preferably 20 to 80% by mass in the solid content of the emulsion (A). More preferred is 30 to 70% by mass.
  • the content of the polymer is less than 10% by mass, when water adheres or when it is boiled with water, water resistance such as whitening or loss of adhesion to the heat-shrinkable film is reduced, When the content of the coalescence exceeds 90% by mass, the effect of improving the adhesion to the film substrate, particularly the polyester resin tends to be small.
  • an epoxy group-containing ⁇ , ⁇ -ethylenically unsaturated compound such as glycidyl (meth) acrylate, a polyfunctional vinyl compound (ethylene glycol di (meth) acrylate, Introducing trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate, etc.) to cross-link themselves or combine with an ethylenically unsaturated compound component having an active hydrogen group Or by introducing a carbonyl group-containing ⁇ , ⁇ -ethylenically unsaturated compound (especially limited to those containing a keto group) and a polyhydrazine compound (especially a compound having two or more hydrazide groups; oxalic acid dihydrazide, succinic acid) Acid dihydrazide, adipic acid dihydrazide, polyacrylic It is also possible to introduce a carbonyl group-containing ⁇ , ⁇ -ethy
  • the glass transition temperature of the polymer comprising the ethylenically unsaturated monomer in the emulsion (A) is preferably 0 to 60 ° C, more preferably 10 to 50 ° C, and more preferably 20 to 40 ° C. More preferably.
  • the glass transition temperature of a polymer composed of an ethylenically unsaturated monomer is less than 0 ° C, there is concern about a decrease in wear resistance and water resistance, and when the glass transition temperature is higher than 60 ° C, film formability is high. In some cases, adhesion to the substrate, transmittance, and haze may decrease.
  • the glass transition temperature here is a value calculated from the Fox equation.
  • the water-soluble polyester or water-dispersible polyester those produced from polybasic acid and polyol are used, and the production method is not limited at all.
  • the water-soluble polyester means one that is completely soluble in water at 23 ° C.
  • a water-dispersible polyester has a hydrophobic part (hydrophobic part) and a hydrophilic part (hydrophilic part) in the polyester molecule.
  • the hydrophilic part is surrounded by a hydrophobic part in water.
  • the polybasic acid component is, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, etc., and these may be used alone. Two or more kinds may be used in combination.
  • polyol component examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, bisphenol, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • a water-dispersible polyester in which the polybasic acid component is terephthalic acid or isophthalic acid and the polyol component is ethylene glycol, propylene glycol, or 1,6-hexanediol is preferable from the viewpoint of water dispersion stability.
  • a component having a hydrophilic group such as a carboxyl group or a sulfonic acid group may be copolymerized.
  • (anhydrous) trimellitic acid in order to introduce a carboxyl group into a polyester molecule, for example, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, trimesic acid and the like are used, and the resulting polymer is converted to an amino compound, What is necessary is just to neutralize with ammonia or an alkali metal.
  • (anhydrous) trimellitic acid is preferable from the viewpoint of water solubility or water dispersibility.
  • water dispersibility can be imparted to the polyester resin.
  • the neutralization dissociates the carboxyl group into a carboxylate anion, which contributes to stabilization of dispersion in water by imparting solubility and ionic repulsion at the water-resin interface.
  • alkali metal salts such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, Ammonium salts are used.
  • alkali metal salts such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, Ammonium salts are used.
  • 1,3-dimethyl 5-sulfoisophthalate is preferable from the viewpoint of water solubility or water dispersibility.
  • water-soluble polyester or water-dispersible polyester used in the present invention commercially available ones may be used as they are, for example, plus coat (registered trademark) Z-221, Z-446, Z-561, Z-687, Z-565, Z-690, RZ-105, RZ-570, Z-730, Z-732, and Z-735 (manufactured by Kyoyo Chemical Co., Ltd.), Pesresin (registered trademark) A-110, A-210, And A-620 (manufactured by Takamatsu Yushi Co., Ltd.), Bayronal (registered trademark) MD-1200, MD-1220, MD-1250, MD-1335, MD-1400, MD-1480 and MD-1500 (manufactured by Toyobo Co., Ltd.) ) And the like.
  • plus coat Z-221, Z-446, Z-561, Z-687, Z-565, Z-690, RZ-105, RZ-570, Z-730, Z-732, and Z-735
  • the glass transition temperature of the water-soluble polyester or water-dispersible polyester used in the present invention is preferably 30 to 80 ° C., more preferably 35 to 75 ° C. in consideration of water resistance, durability and film formability. Preferably, the temperature is 40 to 70 ° C. If the glass transition temperature of the water-soluble polyester or water-dispersible polyester is lower than 30 ° C., the wear resistance and water resistance may be lowered. Adhesion, transmittance and haze may be reduced.
  • the glass transition temperature of water-soluble polyester or water-dispersible polyester can be measured, for example, by differential scanning calorimetry (DSC).
  • the polymerization reaction of the ethylenically unsaturated monomer is carried out by any one of a batch type, a semi-continuous type and a continuous type using an atmospheric pressure reactor or a pressure resistant reactor.
  • the reaction temperature is usually 10 to 100 ° C., but 30 to 90 ° C. is common.
  • the reaction time is not particularly limited, and may be appropriately adjusted according to the amount of each component and the reaction temperature.
  • Examples of the emulsifier used for such radical polymerization include nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and alkyl sulfate esters. And anionic surfactants such as alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, polyoxyalkylene alkyl sulfate, and polyoxyalkylene alkyl phosphate. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the polymerization initiator used in the emulsion polymerization may be a known and conventional one, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, and t-butyl hydroperoxide. Further, if necessary, these polymerization initiators may be combined with sodium sulfoxylate formaldehyde, ascorbic acid, sulfite, tartaric acid or salts thereof for redox polymerization. Moreover, you may use alcohol and mercaptans as a chain transfer agent as needed.
  • the wax-based lubricant (B) used in the present invention has a property of improving the wear resistance of the wear-resistant layer when an aqueous coating material is applied to a substrate.
  • the hardness of the applied polymer is not sufficient, and it is necessary to impart slipperiness by adding a wax-based lubricant (B).
  • the wax-based lubricant (B) include polyethylene wax, polypropylene wax, oxides thereof, modified products such as derivatives having these carboxyl groups, paraffin wax, microcrystalline wax, carnauba wax, and the like.
  • examples include wax dispersed in water, or emulsion type wax emulsified by self-emulsification or emulsification.
  • polyolefin waxes such as polyethylene wax and polypropylene wax are preferable, and polyethylene wax is more preferable because the effect of improving the wear resistance of the wear resistant layer is excellent.
  • the melting point of polyethylene wax or polypropylene wax is preferably 90 to 160 ° C, more preferably 100 to 150 ° C, and further preferably 110 to 140 ° C.
  • the content of the wax-based lubricant (B) is a resin comprising an emulsion resin (that is, a resin obtained by polymerizing a water-soluble polyester or water-dispersible polyester and an ethylenically unsaturated monomer). %) To 1 to 30% by mass in terms of solid content. It is more preferably 5 to 25% by mass, and further preferably 10 to 20% by mass.
  • the wear resistance is weak, and when it exceeds 30% by mass, film adhesion, transparency and haze may be lowered.
  • the wax-based lubricant (B) may be a known one, and is not particularly limited.
  • Examples of commercially available products include Hitec (registered trademark) E-6400, E-1000, E-2213, and E-9015. , E-6000S (manufactured by Toho Chemical Co., Ltd.), Polylon (registered trademark) P-502, L-618 (manufactured by Chukyo Yushi Co., Ltd.), AQUACER (registered trademark) 498, 515, 531, 537, 539, and 593 (Manufactured by Big Chemie Japan Co., Ltd.), EMUSTAR (registered trademark) 0443, 0436, 1155, 0135, 0136 (manufactured by Nippon Seiki Co., Ltd.) and the like.
  • the coating material thus obtained is a resin component such as an acrylic resin, an ethylene-vinyl acetate resin, a vinyl acetate resin, an epoxy resin, an amino resin, and a urethane resin, as long as the effects of the present invention are not impaired.
  • a resin component such as an acrylic resin, an ethylene-vinyl acetate resin, a vinyl acetate resin, an epoxy resin, an amino resin, and a urethane resin, as long as the effects of the present invention are not impaired.
  • it can be used as a coating material by making a paint using extender pigments or colored pigments.
  • the coating material of the present invention can be applied to a substrate by a conventionally known coating method such as a gravure coating method, a rod coating method, a spray coating method, an air knife coating method or a roll coating method, and is not particularly limited.
  • the coating amount of the coating material applied to the film substrate is about 0.01 to 10 g / m 2 , preferably about 0.05 to 5 g / m 2 , more preferably 0.1 to 3 g / m 2 in terms of solid content. Degree. When the coating amount of the coating material exceeds 10 g / m 2 , the adhesion of the wear resistant layer at the time of film shrinkage is deteriorated. When the coating amount of the coating material is less than 0.01 g / m 2 , wear resistance cannot be obtained.
  • the heat-shrinkable film of the present invention can be stretched at least in a uniaxial direction after a coating material is applied to a film substrate.
  • a coating material is applied to a film substrate.
  • the stretching method is not particularly limited, and a known stretching method such as a tubular stretching method, a tenter stretching method, or a roll stretching method can be used. In any of these methods, a sequential biaxial stretching method or a simultaneous 2 stretching method can be used.
  • the film can be stretched by an axial stretching method, a monoaxial stretching method, or a combination thereof.
  • the surface on the side where the coating material is applied to the film substrate may be a polyester resin or a polystyrene resin.
  • the film substrate may be a laminated film or multilayer film with a polyester resin, polystyrene resin, polyolefin resin, nylon resin, or the like.
  • Examples of the laminated film and multilayer film include polyester resins / polystyrene resins, polyester resins / polyolefin resins, polystyrene resins / polyolefin resins, polyester resins / nylon resins, polystyrene resins / nylon resins.
  • the laminated film or multilayer film may have an adhesive layer between each layer.
  • the adhesive layer is not particularly limited, and a commercially available adhesive resin or a mixture of the resins can be used.
  • polyester-based resin used for the film substrate for example, a resin obtained by polycondensation of dicarboxylic acid and diol can be used.
  • dicarboxylic acid used to obtain the polyester resin examples include o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octyl succinic acid, cyclohexanedicarboxylic acid, and naphthalene dicarboxylic acid.
  • dicarboxylic acid examples include acids, fumaric acid, maleic acid, itaconic acid, decamethylene carboxylic acid, anhydrides thereof, and lower alkyl esters.
  • diol used to obtain the polyester resin examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, Propylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), Aliphatic such as 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol Diols; 2,2-bis (4-hydroxycyclohexyl) propyl Bread, 2,2-bis (4-hydroxycyclohexyl
  • polystyrene-based resin used for the film substrate examples include aromatic vinyl hydrocarbon-conjugated diene copolymer, or aromatic vinyl hydrocarbon-conjugated diene copolymer and aromatic vinyl hydrocarbon-aliphatic unsaturated.
  • examples thereof include a mixed resin with a carboxylic acid ester copolymer and rubber-modified impact-resistant polystyrene. Since the aromatic vinyl hydrocarbon-conjugated diene copolymer is excellent in low-temperature shrinkage, the resulting heat-shrinkable multilayer label can be easily attached to a container without generating wrinkles or the like. In addition, the shrink finish is excellent.
  • the shrink finish is excellent. Also, when rubber-modified impact-resistant polystyrene is used, the shrink finish is excellent.
  • aromatic vinyl hydrocarbon-conjugated diene copolymer is not particularly limited.
  • aromatic vinyl hydrocarbons include styrene, o-methylstyrene, p-methylstyrene, and conjugated dienes are 1,3- Examples include butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. These may be used alone or in combination of two or more. Of these, a styrene-butadiene-styrene copolymer (SBS resin) is preferred because it is particularly excellent in low-temperature shrinkage and perforation.
  • SBS resin styrene-butadiene-styrene copolymer
  • SIS resin styrene-isoprene-styrene copolymer
  • SIBS resin butadiene-styrene copolymer
  • the aromatic vinyl hydrocarbon-conjugated diene copolymer When the SBS resin, SIS resin or SIBS resin is used as the aromatic vinyl hydrocarbon-conjugated diene copolymer, one kind of resin may be used alone, or a plurality of resins may be used in combination. . When used in plural, dry blending may be used, or a compound resin that is kneaded and pelletized using an extruder with a specific composition may be used. It is preferable to use such a resin singly or in combination as a composition having a styrene content of 65 to 90% by mass and a conjugated diene content of 10 to 35% by mass. A resin having such a composition is particularly excellent in low-temperature shrinkage and perforation.
  • the conjugated diene content is less than 10% by mass, the film is easily cut when tension is applied to the film, and the film may break unexpectedly when used as a converting or label for printing or the like. . If the conjugated diene content exceeds 35% by mass, foreign substances such as gel may be easily generated during the molding process.
  • the aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer is not particularly limited, and examples of the aromatic vinyl hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, and the like.
  • examples of the acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These may be used alone or in combination of two or more.
  • the aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer When a styrene-butyl acrylate copolymer is used as the aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer, the styrene content is 60 to 90% by mass, and the butyl acrylate content is 10 to 40. It is preferable to use what is mass%.
  • the aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer having such a composition By using the aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer having such a composition, a heat-shrinkable multilayer label excellent in shrink finish and perforation cutting property can be obtained.
  • the blending ratio of the aromatic vinyl hydrocarbon-conjugated diene copolymer to the aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer is aromatic vinyl hydrocarbon-conjugated diene copolymer 20-99. % By weight, 1-80% by weight of an aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer. Within this range, the natural shrinkage rate can be effectively suppressed, and a sufficient heat shrinkage rate can be obtained.
  • the rubber-modified impact-resistant polystyrene is composed of a continuous phase composed of a terpolymer of styrene, alkyl methacrylate and alkyl acrylate, and a dispersed phase composed of a rubber component mainly composed of conjugated diene.
  • Basic examples of the alkyl methacrylate forming the continuous phase include methyl methacrylate and ethyl methacrylate, and examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate.
  • the proportion of styrene in the copolymer forming the continuous phase is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
  • the proportion of the alkyl methacrylate is preferably 10 to 50% by mass, more preferably 15 to 40% by mass.
  • the proportion of alkyl acrylate is preferably 1 to 30% by mass, more preferably 5 to 20% by mass.
  • the rubber component mainly composed of conjugated diene forming the dispersed phase is preferably polybutadiene or a styrene-butadiene copolymer having a styrene content of 5 to 30% by mass.
  • the particle size of the rubber component mainly composed of conjugated diene in the dispersed phase is preferably 0.1 to 1.2 ⁇ m, more preferably 0.3 to 0.8 ⁇ m.
  • the particle size of the dispersed phase is less than 0.1 ⁇ m, the impact resistance may be insufficient, and when it exceeds 1.2 ⁇ m, the transparency of the intermediate layer may be lowered.
  • the ratio of the continuous phase composed of a terpolymer of styrene, alkyl methacrylate and alkyl acrylate is preferably 70 to 95% by mass, and the ratio of the dispersed phase composed of a rubber component mainly composed of conjugated diene is preferably 5 to 20% by mass. . If the proportion of the dispersed phase is less than 5% by mass, the impact resistance may be insufficient, and if it exceeds 20% by mass, the transparency of the intermediate layer may be deteriorated.
  • the total thickness (including the base material and the wear-resistant layer) of the heat-shrinkable film of the present invention is about 10 to 100 ⁇ m, preferably about 20 to 80 ⁇ m, more preferably about 25 to 70 ⁇ m. is there.
  • Example 1 Preparation of coating material In a four-necked flask reactor equipped with a stirrer, a thermometer and a reflux condenser, plus coat Z-561 (non-volatile content 25% by mass, sulfonic acid group-containing type) as a water-dispersible polyester , Glass transition temperature 64 ° C.) 840 parts by mass and ion-exchanged water 29 parts by mass were charged, and the temperature was raised to 80 ° C. As the ethylenically unsaturated monomer composition, 58.5 parts by mass of methyl methacrylate and 31.5 parts by mass of butyl acrylate were mixed in advance and prepared.
  • Z-561 non-volatile content 25% by mass, sulfonic acid group-containing type
  • A-1 a copolymer emulsion of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 30.7% by mass, a viscosity of 40 mPa ⁇ s, and a pH of 4.3. Further, the glass transition temperature of the polymer obtained by polymerizing the ethylenically unsaturated monomer, calculated by the Fox equation, was about 30 ° C.
  • the amount of polyester was 70% by mass in the copolymer emulsion in terms of solid content.
  • Step 2 Molding of film base material
  • terephthalic acid is used as a dicarboxylic acid component
  • 67 mol% of a component derived from ethylene glycol is used as a diol component
  • 1,4-cyclohexanedi A polyester resin containing 33 mol% of a component derived from methanol was used. This resin was put into an extruder having a barrel temperature of 200 to 250 ° C., extruded into a sheet form from a multilayer die at 250 ° C., and cooled and solidified by a take-up roll at 25 ° C.
  • Step 3 Production of heat-shrinkable film
  • the obtained film substrate was 1.05 in the film flow direction (hereinafter referred to as MD direction) between the 80 ° C. low-speed roll and the 85 ° C. high-speed roll in the roll stretching machine.
  • the aqueous coating material adjusted in the above (Step 1) was applied by a gravure method and dried through a drying furnace at 60 ° C.
  • the film base material to which the aqueous coating material is applied is 5.0 in a direction (hereinafter, TD direction) perpendicular to the film flow direction in a tenter stretching machine having a preheating zone of 100 ° C., a stretching zone of 90 ° C., and a fixed zone of 80 ° C.
  • Example 2 Except having changed (process 2) and (process 3) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • Step 2 Molding of Film Base
  • a styrene-based resin a styrene-butadiene block copolymer (styrene 78% by mass, butadiene 22% by mass: Vicat softening point 72 ° C., MFR 5.6 g / 10) Min) was used.
  • This resin was put into an extruder having a barrel temperature of 150 to 200 ° C., extruded from a multilayer die at 200 ° C. into a sheet, and cooled and solidified by a take-up roll at 25 ° C.
  • Step 3 Production of heat-shrinkable film After the film base obtained was stretched 1.3 times in the MD direction between a low-speed roll at 80 ° C. and a high-speed roll at 85 ° C. in a roll stretching machine.
  • the aqueous coating material adjusted in the above (Step 1) was applied by a gravure method and dried through a drying furnace at 60 ° C.
  • the film substrate coated with the aqueous coating material was stretched 5.0 times in the TD direction in a tenter stretching machine having a preheating zone of 110 ° C., a stretching zone of 90 ° C., and a fixed zone of 80 ° C.
  • the obtained heat-shrinkable film had a total thickness of about 45 ⁇ m, and the coating amount of the coating material was 1.0 g / m 2 in terms of solid content.
  • Table 1 The evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 1. Note that (Step 2) film base molding and (Step 3) heat-shrinkable film production were performed as a series of steps.
  • Example 3 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 1.
  • Step 1 Preparation of coating material
  • As the ethylenically unsaturated monomer composition 175.5 parts by mass of methyl methacrylate and 94.5 parts by mass of butyl acrylate were mixed in advance and adjusted.
  • A-2 a copolymer emulsion of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 30.1% by mass, a viscosity of 25 mPa ⁇ s, and a pH of 3.9. Further, the glass transition temperature of the polymer obtained by polymerizing the ethylenically unsaturated monomer, calculated by the Fox equation, was about 30 ° C.
  • the amount of polyester was 10% by mass in the copolymer emulsion in terms of solid content.
  • Example 4 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 1.
  • Step 1 Preparation of coating material
  • the ethylenically unsaturated monomer composition 117.0 parts by mass of methyl methacrylate and 63.0 parts by mass of butyl acrylate were mixed in advance and prepared.
  • A-3 a copolymer emulsion of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 30.7% by mass, a viscosity of 30 mPa ⁇ s, and a pH of 3.5. Further, the glass transition temperature of the polymer obtained by polymerizing the ethylenically unsaturated monomer, calculated by the Fox equation, was about 30 ° C.
  • the amount of polyester was 40% by mass in the copolymer emulsion in terms of solid content.
  • Example 5 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 1.
  • Step 1 Preparation of coating material
  • the ethylenically unsaturated monomer composition 19.5 parts by mass of methyl methacrylate and 10.5 parts by mass of butyl acrylate were mixed in advance and prepared.
  • A-4 a copolymer emulsion of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 27.4% by mass, a viscosity of 10 mPa ⁇ s, and a pH of 3.1. Further, the glass transition temperature of the polymer obtained by polymerizing the ethylenically unsaturated monomer, calculated by the Fox equation, was about 30 ° C. In addition, the amount of polyester was 90 mass% in copolymerization emulsion in conversion of solid content.
  • Example 6 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 2.
  • Step 1 Preparation of coating material
  • pesresin A-515GE non-volatile content: 30% by mass, sulfonic acid group-containing type, Glass transition temperature 35 ° C.
  • 840 parts by mass and ion-exchanged water 169 parts by mass were charged, and the temperature was raised to 80 ° C.
  • the ethylenically unsaturated monomer composition 58.5 parts by mass of methyl methacrylate and 31.5 parts by mass of butyl acrylate were mixed in advance and prepared.
  • a film forming aid 60 parts by mass of propylene glycol n-butyl ether was added to obtain a copolymer emulsion (A-5) of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 30.5% by mass, a viscosity of 30 mPa ⁇ s, and a pH of 4.5. Further, the glass transition temperature of the polymer obtained by polymerizing the ethylenically unsaturated monomer, calculated by the Fox equation, was about 30 ° C.
  • the amount of polyester was 70% by mass in the copolymer emulsion in terms of solid content.
  • wax-based lubricant (B) To 100 parts by weight of copolymer emulsion (A-5), 10 parts by weight of polyethylene wax emulsion (Hitech E-6400, Toho Chemical Co., Ltd., 35% non-volatile content, melting point 120 ° C.) as wax-based lubricant (B) is added. did. The amount of the wax-based lubricant (B) was 11.7% by mass in terms of solid content with respect to the resin content of the emulsion.
  • Example 7 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 2.
  • Step 1 Preparation of coating material In a four-necked flask reactor equipped with a stirrer, a thermometer and a reflux condenser, plus coat Z-561 (non-volatile content 25% by mass, sulfonic acid group-containing type) as a water-dispersible polyester , Glass transition temperature 64 ° C.) 529 parts by mass, plus coat Z-690 (nonvolatile content 25% by mass, carboxylic acid group-containing type, glass transition temperature 110 ° C.) 311 parts by mass, ion-exchanged water 29 parts by mass, 80 ° C. The temperature was raised to.
  • ethylenically unsaturated monomer composition 58.5 parts by mass of methyl methacrylate and 31.5 parts by mass of butyl acrylate were mixed in advance and prepared. 0.5 parts by mass of potassium persulfate was added to the reactor, and at the same time, the ethylenically unsaturated monomer composition was also dropped. In addition, dropwise addition of 0.75 part by mass of potassium persulfate with 43.8 parts by mass of ion-exchanged water was started. The ethylenically unsaturated monomer composition and the polymerization initiator were added dropwise over 2 hours. The temperature inside the reactor during the dropping was kept at 80 ° C.
  • the mixture was kept at 80 ° C. for 1 hour and then cooled to room temperature.
  • 100 parts by mass of propylene glycol n-butyl ether was added to obtain a copolymer emulsion (A-6) of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 31.0% by mass, a viscosity of 30 mPa ⁇ s, and a pH of 4.1.
  • the amount of polyester was 70% by mass in the copolymer emulsion in terms of solid content.
  • A-6 10 parts by weight of polyethylene wax emulsion (Hitech E-6400 manufactured by Toho Chemical Industry Co., Ltd., non-volatile content 35%, melting point 120 ° C.) as a wax-based lubricant (B) is added. did.
  • the amount of the wax-based lubricant (B) was 11.7% by mass in terms of solid content with respect to the resin content of the emulsion.
  • Example 8 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 2.
  • Step 1 Preparation of coating material
  • As the ethylenically unsaturated monomer composition 41.5 parts by mass of methyl methacrylate and 48.5 parts by mass of butyl acrylate were mixed in advance and prepared.
  • A-7 a copolymer emulsion of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 30.0% by mass, a viscosity of 35 mPa ⁇ s, and a pH of 4.3. Further, the glass transition temperature of the polymer obtained by polymerizing the ethylenically unsaturated monomer, calculated by the Fox equation, was about 0 ° C.
  • the amount of polyester was 70% by mass in the copolymer emulsion in terms of solid content.
  • Example 9 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • the evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 2.
  • Step 1 Preparation of coating material
  • As an ethylenically unsaturated monomer composition 73.0 parts by mass of methyl methacrylate and 17.0 parts by mass of butyl acrylate were mixed in advance and prepared.
  • a copolymer emulsion (A-8) of an ethylenically unsaturated monomer 80 parts by mass of propylene glycol n-butyl ether was added to obtain a copolymer emulsion (A-8) of an ethylenically unsaturated monomer.
  • the properties were a non-volatile content of 30.3% by mass, a viscosity of 45 mPa ⁇ s, and a pH of 4.0.
  • the amount of polyester was 70% by mass in the copolymer emulsion in terms of solid content.
  • copolymer emulsion (A-8) To 100 parts by weight of copolymer emulsion (A-8), 10 parts by weight of polyethylene wax emulsion (Hitech E-6400, 35% non-volatile content, melting point 120 ° C., manufactured by Toho Chemical Industry Co., Ltd.) is added as a wax-based lubricant (B). did. The amount of the wax-based lubricant (B) was 11.7% by mass in terms of solid content with respect to the resin content of the emulsion.
  • polyethylene wax emulsion Hitech E-6400, 35% non-volatile content, melting point 120 ° C., manufactured by Toho Chemical Industry Co., Ltd.
  • the amount of the wax-based lubricant (B) was 11.7% by mass in terms of solid content with respect to the resin content of the emulsion.
  • Example 10 Except having changed (process 1) and (process 3) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • Example 1 except that 10 parts by mass of paraffin wax emulsion (AQUACER-539 manufactured by Big Chemie Japan Co., Ltd., non-volatile content 35%, melting point 90 ° C.) was added as the wax-based lubricant (B) used in (Step 1). The same operation was performed to obtain a heat shrinkable film. The amount of the wax-based lubricant (B) was 11.7% by mass in terms of solid content with respect to the resin content of the emulsion.
  • paraffin wax emulsion AQUACER-539 manufactured by Big Chemie Japan Co., Ltd., non-volatile content 35%, melting point 90 ° C.
  • the film base material obtained in (Step 3) was coated with the aqueous coating material adjusted in (Step 1) by a gravure method and dried through a drying furnace at 60 ° C.
  • the film base material coated with the aqueous coating material is stretched 1.05 times in the MD direction between a low-speed roll at 80 ° C. and a high-speed roll at 85 ° C. in a roll stretching machine, and then preheated in a tenter stretching machine.
  • the film was stretched 5.0 times in the TD direction at a zone of 100 ° C, a stretching zone of 90 ° C, and a fixed zone of 80 ° C.
  • the obtained heat-shrinkable film had a total thickness of about 45 ⁇ m and a coating material coating amount of 0.7 g / m 2 .
  • Table 2 The evaluation results of each characteristic of the obtained heat-shrinkable film are shown in Table 2.
  • Example 11 Except having changed (process 1) into the following, operation similar to Example 1 was performed and the heat-shrinkable film was obtained.
  • Example 10 except that 10 parts by weight of a polypropylene wax emulsion (AQUACER-593 manufactured by Big Chemie Japan Co., Ltd., non-volatile content 30%, melting point 160 ° C.) was added as the wax-based lubricant (B) used in (Step 1). Operation was performed to obtain a heat-shrinkable film. The amount of the wax-based lubricant (B) was 13.7% by mass in terms of solid content with respect to the resin content of the emulsion. Table 3 shows the evaluation results of the characteristics of the obtained heat-shrinkable film.
  • AQUACER-593 manufactured by Big Chemie Japan Co., Ltd., non-volatile content 30%, melting point 160 ° C.
  • Example 12 Example 1 except that 25 parts by mass of polyethylene wax emulsion (Hitech E-6400, non-volatile content 35%, melting point 120 ° C.) manufactured by Toho Chemical Industry Co., Ltd. was added as the wax-based lubricant (B) used in (Step 1). The same operation was performed to obtain a heat shrinkable film. The amount of the wax-based lubricant (B) was 29.1% by mass in terms of solid content with respect to the resin content of the emulsion. Table 3 shows the evaluation results of the characteristics of the obtained heat-shrinkable film.
  • polyethylene wax emulsion Hitech E-6400, non-volatile content 35%, melting point 120 ° C.
  • Table 3 shows the evaluation results of the characteristics of the obtained heat-shrinkable film.
  • Example 13 Example 1 except that 1 part by weight of a polyethylene wax emulsion (Hitech E-6400, non-volatile content 35%, melting point 120 ° C.) manufactured by Toho Chemical Co., Ltd. was added as the wax-based lubricant (B) used in (Step 1). Thus, a heat-shrinkable film was obtained.
  • the amount of the wax-based lubricant (B) was 1.2% by mass in terms of solid content with respect to the resin content of the emulsion.
  • Table 3 shows the evaluation results of the characteristics of the obtained heat-shrinkable film.
  • Step 1 Preparation of coating material 100 parts by weight of (meth) acrylic acid ester copolymer emulsion (Polysol AP-4690, Showa Denko KK, nonvolatile content 35%, viscosity 50 mPa ⁇ s, glass transition temperature 15 ° C.) 10 parts by mass of a polyethylene wax emulsion (Hitech E-6400 manufactured by Toho Chemical Industry Co., Ltd., non-volatile content 35%, melting point 120 ° C.) was added.
  • (meth) acrylic acid ester copolymer emulsion Polysol AP-4690, Showa Denko KK, nonvolatile content 35%, viscosity 50 mPa ⁇ s, glass transition temperature 15 ° C.
  • a polyethylene wax emulsion Hitech E-6400 manufactured by Toho Chemical Industry Co., Ltd., non-volatile content 35%, melting point 120 ° C.
  • Step 1 Preparation of coating material Water-dispersible polyester emulsion (Plus coat Z-561 manufactured by Kyoyo Chemical Industry Co., Ltd., nonvolatile content 25% by mass, sulfonic acid group-containing type, glass transition temperature 64 ° C., acid value 2.5) To 100 parts by mass, 10 parts by mass of polyethylene wax emulsion (Hitech E-6000S manufactured by Toho Chemical Industry Co., Ltd., nonvolatile content 35%, melting point 140 ° C.) was added.
  • Polyethylene wax emulsion Hitech E-6000S manufactured by Toho Chemical Industry Co., Ltd., nonvolatile content 35%, melting point 140 ° C.
  • a cellophane tape transparent pressure-sensitive adhesive tape compliant with JIS5600-5-6
  • the wear-resistant layer the surface of the heat-shrinkable film coated with a water-based coating material. It peeled at a stretch and evaluated adhesiveness. Whether or not the abrasion-resistant layer was peeled off by the cellophane tape was judged by visual observation, and those that did not peel at all were considered to have good adhesion.
  • a heat-shrinkable film is mounted on a polyacetal jig having a conical shape with a wear-resistant layer as an outer surface using tape or the like, and the apex of the conical jig is placed on the cardboard ( KOKUYO Campus (medium 430 g / m 2 ). At this time, the wear-resistant layer of the film was brought into contact with the cardboard.
  • the jig was slid parallel to the cardboard at a speed of 3000 mm / sec and a moving distance of 45 mm under the condition of 65% humidity, and the number of sliding times until a pinhole was formed was counted.
  • the occurrence of pinholes was determined by whether or not the penetrating solution was dropped onto the heat-shrinkable film where the apex of the jig had hit and permeated on white paper. For eight samples, the number of sliding until a pinhole was formed was measured, and the average value was calculated. When the number of sliding times was 350 or more, the wear resistance was good.
  • the heat-shrinkable film was cut into a size of 3 cm ⁇ 10 cm, and 10 samples were collected. At this time, it was clarified so that it can be understood which side of the film is a wear-resistant layer surface and a printed surface (non-abrasion-resistant layer). 2 on a 3 cm ⁇ 16 cm straw half paper so that the wear-resistant layer surface (coated surface) and the opposite surface (printing surface) of the two heat-shrinkable films face each other, and the center width of the straw half paper is 2 cm in the longitudinal direction.
  • Sheets of heat-shrinkable film were set so as to overlap each other, and a straw half paper was further stacked thereon so that the positions of the four sides of the two straw half papers were not shifted.
  • one short side of the straw half paper and one short side of the heat shrinkable film are overlapped at the same position
  • the other short side of the straw half paper and one short side of another heat shrinkable film are overlapped at the same position
  • the heat-shrinkable film overlaps with an area of 3 cm ⁇ 4 cm at a position closer to the center than 6 cm along the longitudinal direction from both short sides of the straw half paper, and the straw half paper is further stacked thereon.
  • the heat-shrinkable properties of the two sheets were made with the wear-resistant layer surface and the wear-resistant layer surface facing each other.
  • Five layers of film and straw semi-paper were stacked, and the upper and lower surfaces became straw semi-paper to make a blocking measurement sample. This was sandwiched between two pieces of 3 cm ⁇ 16 cm thick paper, and both ends were fastened with eyeball clips, and a 600 g weight was set on the thick paper. This was left to stand in a constant temperature bath at 40 ° C.
  • the value of peel strength was read as “g”, and 0.25 kg / 3 cm ⁇ 4 cm or less was regarded as good blocking property.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un film thermorétractable ayant une meilleure résistance à l'abrasion et à une étiquette thermorétractable utilisant le film. Le film thermorétractable est caractérisé en ce qu'il est obtenu par le revêtement d'un substrat de film constitué d'une résine de polyester ou d'une résine de polystyrène à l'aide d'un matériau de revêtement aqueux constitué d'une émulsion (A), qui comprend un polymère d'un monomère non saturé éthylénique dont le colloïde protecteur est un polyester soluble dans l'eau ou un polyester dispersible dans l'eau, et d'un lubrifiant à base de cire (B). De préférence, le lubrifiant à base de cire (B) est une cire de polyéthylène ou une cire de polypropylène et a un point de fusion compris entre 90 et 160 ºC.
PCT/JP2012/066888 2011-07-19 2012-07-02 Film thermorétractable et étiquette thermorétractable WO2013011826A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2015182451A1 (fr) * 2014-05-27 2015-12-03 グンゼ株式会社 Film multicouche thermorétractable, fabrication d'un film multicouche thermorétractable, et étiquette thermorétractable
JP2016222783A (ja) * 2015-05-28 2016-12-28 グンゼ株式会社 熱収縮性フィルム
CN113291025A (zh) * 2021-06-02 2021-08-24 山东圣和薄膜新材料有限公司 一种可回收的收缩膜及其制备方法

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JP2002327149A (ja) * 2001-04-27 2002-11-15 Fuji Seal Inc プラスチックラベル用コーティング剤組成物及び該コーティング剤組成物が塗布されたプラスチックラベル
JP2005047958A (ja) * 2003-07-29 2005-02-24 Toyobo Co Ltd 熱収縮性ポリエステル系フイルム
JP2011105788A (ja) * 2009-11-12 2011-06-02 Showa Denko Kk プラスチックコーティング用水性樹脂エマルジョン

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JP2002132159A (ja) * 2000-10-19 2002-05-09 Fuji Seal Inc 防傷性及び防汚性に優れたオレフィン系熱収縮性ラベル
JP2006181897A (ja) * 2004-12-28 2006-07-13 Toyobo Co Ltd 熱収縮性ポリエステル系フィルム及びその製造方法、熱収縮性ラベル

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JP2002327149A (ja) * 2001-04-27 2002-11-15 Fuji Seal Inc プラスチックラベル用コーティング剤組成物及び該コーティング剤組成物が塗布されたプラスチックラベル
JP2005047958A (ja) * 2003-07-29 2005-02-24 Toyobo Co Ltd 熱収縮性ポリエステル系フイルム
JP2011105788A (ja) * 2009-11-12 2011-06-02 Showa Denko Kk プラスチックコーティング用水性樹脂エマルジョン

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015182451A1 (fr) * 2014-05-27 2015-12-03 グンゼ株式会社 Film multicouche thermorétractable, fabrication d'un film multicouche thermorétractable, et étiquette thermorétractable
JPWO2015182451A1 (ja) * 2014-05-27 2017-04-20 グンゼ株式会社 熱収縮性多層フィルム、熱収縮性多層フィルムの製造方法、及び、熱収縮性ラベル
JP2016222783A (ja) * 2015-05-28 2016-12-28 グンゼ株式会社 熱収縮性フィルム
CN113291025A (zh) * 2021-06-02 2021-08-24 山东圣和薄膜新材料有限公司 一种可回收的收缩膜及其制备方法

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