WO2019073702A1 - 透明積層体 - Google Patents

透明積層体 Download PDF

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Publication number
WO2019073702A1
WO2019073702A1 PCT/JP2018/031218 JP2018031218W WO2019073702A1 WO 2019073702 A1 WO2019073702 A1 WO 2019073702A1 JP 2018031218 W JP2018031218 W JP 2018031218W WO 2019073702 A1 WO2019073702 A1 WO 2019073702A1
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WO
WIPO (PCT)
Prior art keywords
layer
adhesive
transparent laminate
absorber
ultraviolet absorber
Prior art date
Application number
PCT/JP2018/031218
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English (en)
French (fr)
Japanese (ja)
Inventor
晋久 岩崎
白根　隆志
針田　紀子
Original Assignee
共同印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 共同印刷株式会社 filed Critical 共同印刷株式会社
Priority to SG11202001496RA priority Critical patent/SG11202001496RA/en
Priority to MYPI2020001000A priority patent/MY194442A/en
Publication of WO2019073702A1 publication Critical patent/WO2019073702A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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

Definitions

  • the present invention relates to a transparent laminate.
  • a transparent container In the fields of cosmetics, medicines, foods, etc., a transparent container may be used which allows the contents to be visible from the outside. When using a transparent container, in order to protect the contents from ultraviolet light, it is desirable to provide the container material with an ultraviolet absorbing ability.
  • Patent Document 1 describes that an ultraviolet absorber is added to the outermost layer of the laminated sheet constituting the transparent container.
  • Patent Document 2 describes that a UV light stabilizer is contained in the polyester resin composition layer constituting one layer of the laminate for laminate tube.
  • Patent Document 3 describes that an unstretched thermoplastic resin layer containing an ultraviolet light absorber is used as an outer layer or an inner layer of a packaging container. The techniques described in these patent documents relate to kneading an ultraviolet absorber into one of the laminates that are the material of the transparent container.
  • Patent Document 4 describes a laminated film in which an organic ultraviolet absorber migration inhibiting layer composed of an oxygen atom-containing thermoplastic resin is laminated on both sides of an ultraviolet blocking layer containing an organic ultraviolet absorber.
  • Patent Document 5 describes that a resin composition containing an ultraviolet absorber is applied to form a barrier resin film in a laminated material for forming a laminated tube container. This technology relates to forming an ultraviolet absorbing layer by a coating method.
  • JP 2002-68222 A JP, 2012-116082, A JP 2012-157703 A Unexamined-Japanese-Patent No. 9-239889 JP-A-11-20073
  • UV absorber When organic UV absorbers are used, there is a concern that the UV absorber bleeds out. When the ultraviolet absorber bleeds out due to aging or heating, the adhesion of the ink may be deteriorated when printing is performed on the container, and the lamination strength may be deteriorated when performing dry lamination.
  • an inorganic ultraviolet absorber when used, there is little possibility of bleeding out even if the ultraviolet absorber is kneaded into one layer of the laminate. However, the use of an inorganic UV absorber is not preferable because it may impair the transparency of the resulting laminate.
  • Patent Document 5 In the technology described in Patent Document 5, in which the ultraviolet absorbing layer is formed by the application method, the thickness of the applied layer is limited, so it is considered difficult to set the conditions for expressing the ultraviolet absorbing function. Be Also in Patent Document 5, there is no specific guideline as to the type and content of the ultraviolet light absorbing material contained in the coating solution. Also, the printing method employed when the transparent container is a laminated tube is mostly UV printing. The addition of a UV absorber into the UV ink used for UV printing can cause curing failure of the print layer.
  • an object of the present invention is to provide a transparent laminate having high transparency, printability, and an ultraviolet cut function.
  • the present invention is as follows.
  • ⁇ Aspect 1 Having an outer layer, an adhesive layer, and an inner layer in this order, The adhesive layer contains a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber. Transparent laminate.
  • ⁇ Aspect 2 >> The amount of the benzotriazole-based ultraviolet absorber is 0.10 g / m 2 or more and 0.30 g / m 2 or less per area of the transparent laminate.
  • the amount of the benzophenone-based ultraviolet absorber is 0.10 g / m 2 or more and 2.00 g / m 2 or less per area of the transparent laminate.
  • the transparent laminated body as described in aspect 1.
  • ⁇ Aspect 3 The transparent laminate according to aspect 1 or 2, wherein the outer layer and the inner layer are each a layer having a single-layer structure or a multi-layer structure including an LLDPE film.
  • ⁇ Aspect 4 The transparent laminate according to aspect 3, wherein the inner layer is a layer having a multilayer structure further comprising a PET layer.
  • ⁇ Aspect 5 The adhesive layer is composed of a cured product of a two-component curable UV-absorbing adhesive composition comprising a two-component curable adhesive, a benzotriazole-based UV absorber and a benzophenone-based UV absorber.
  • ⁇ Aspect 6 The transparent laminate according to aspect 5, wherein the curing agent of the two-component curing type adhesive is an aliphatic curing agent.
  • ⁇ Aspect 7 For the above transparent laminate, when the ultraviolet transmittance is measured under the conditions of a measurement wavelength of 200 nm to 500 nm, a scanning speed of 600 nm / min, and a slit width of 4.00 nm, the ultraviolet transmittance at wavelengths of 360 nm, 330 nm, and 270 nm The transparent laminate according to any one of Embodiments 1 to 6, which is also 5.0% or less.
  • ⁇ Aspect 8 >> The transparent laminate according to any one of Aspects 1 to 7, which is used for a tube container.
  • ⁇ Aspect 9 A method for producing a transparent laminate, comprising laminating an outer layer and an inner layer through an adhesive layer containing a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber.
  • ⁇ Aspect 10 By dry lamination using a two-part curable UV-absorbing adhesive composition comprising the above outer layer and the above-mentioned inner layer, a two-part curable adhesive, a benzotriazole-based UV absorber and a benzophenone-based UV absorber The manufacturing method of the transparent laminated body of aspect 9 which laminates
  • ⁇ Aspect 11 Adhesive, Benzotriazole type ultraviolet absorber and benzophenone type ultraviolet absorber; An ultraviolet-absorbing adhesive composition comprising ethyl acetate.
  • ⁇ Aspect 12 The ultraviolet-absorbing adhesive composition according to aspect 11, wherein the adhesive is a two-part curable adhesive.
  • a transparent laminate having high transparency, printability, and an ultraviolet cut function is provided.
  • FIG. 1 is a schematic cross-sectional view for explaining the layer configuration of the transparent laminate of the present invention.
  • FIG. 2 is an ultraviolet ray transmittance chart of the transparent laminate sample obtained in each of Comparative Examples 1 to 3.
  • FIG. 3 is an ultraviolet ray transmission chart of the transparent laminate sample obtained in Example 5.
  • Fig.4 (a) is an ultraviolet-ray transmittance chart before wiping off the surface of the transparent laminated body obtained in Example 13 by ethanol
  • Fig.5 (a) is an ultraviolet-ray transmittance chart before wiping off the back surface of the transparent laminated body obtained in Example 13 by ethanol
  • FIG.5 (b) wiped the back surface of this transparent laminated body with ethanol It is a ultraviolet ray transmittance chart after.
  • the transparent laminate of the present invention is, for example, as shown in FIG. Having an outer layer (1), an adhesive layer (2), and an inner layer (3) in this order,
  • the adhesive layer (2) contains a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber.
  • the present invention is characterized in that the adhesive layer in the transparent laminate contains two types of UV absorbers, a benzotriazole type UV absorber and a benzophenone type UV absorber.
  • the adhesive layer in the transparent laminate is often formed by applying as a solution-like adhesive composition in which an adhesive material is dissolved in a solvent.
  • a solution-like adhesive composition in which an adhesive material is dissolved in a solvent.
  • the resulting adhesive layer is a thin layer, and thus the absolute amount of UV absorber that can be included in the adhesive layer is limited.
  • it is required to block the transmission of a wide range of ultraviolet light.
  • UV absorbers that can block the transmission of a broad range of UV light, but that are soluble in the solvent used in the adhesive composition, or as small as small enough to be included in the adhesive layer of the thin layer No combination of UV absorbers is known in the prior art.
  • the present invention has succeeded in simultaneously meeting all the above requirements by including two types of ultraviolet absorbers, benzotriazole type ultraviolet absorber and benzophenone type ultraviolet absorber, in the adhesive layer in the transparent laminate. It is a thing.
  • the outer layer in the transparent laminate of the present invention may be a transparent resin layer, and in particular, may be a single layer structure or a multilayer structure including a transparent resin layer having heat sealability.
  • the sheet-like transparent laminate is rolled into a cylindrical shape, the end portions of the outer layer and the inner layer are overlapped, and this overlapping portion is heat sealed to form a cylindrical body. There is something to do.
  • the outer layer and the inner layer are heat-sealed so as to fuse, it is preferable that the heat sealability with the inner layer resin be good as the heat sealable transparent resin constituting the outer layer.
  • the transparent resin layer particularly the transparent resin having heat sealability as described above, include polyethylene (PE).
  • PE polyethylene
  • polyethylene may be, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) or the like.
  • the transparent resin having heat sealability may be a sheet of these resins, a film, or a coating film formed using a composition containing these resins, and in particular, may be an LLDPE film.
  • the outer layer may be a single layer or multi-layer layer comprising an LLDPE film.
  • the outer layer in the transparent laminate of the present invention may have, for example, a polyester layer, an inorganic vapor deposition layer, etc. in addition to the transparent resin layer, particularly the LLDPE film.
  • the polyester layer may be, for example, a uniaxial or biaxial stretched film composed of polyethylene terephthalate (PET) or the like.
  • the thickness of the outer layer may be, for example, 20 ⁇ m or more, 40 ⁇ m or more, 60 ⁇ m or more, or 80 ⁇ m or more, and may be, for example, 150 ⁇ m or less, 140 ⁇ m or less, 130 ⁇ m or less, 120 ⁇ m or less, 110 ⁇ m or less, or 100 ⁇ m or less.
  • the adhesive layer of the transparent laminate of the present invention contains both a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber.
  • the adhesive layer in the transparent laminate of the present invention is optional as long as it contains both a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber, and the outer layer and the inner layer can be adhered and laminated. Good.
  • the adhesive layer may be a cured product of an adhesive composition containing a one-component or two-component adhesive.
  • the one-component adhesive may be, for example, a vinyl acetate resin adhesive, an ethylene / vinyl acetate copolymer adhesive, an acrylic resin adhesive, a vinyl chloride resin adhesive, a chloroprene rubber adhesive, etc. .
  • the two-component adhesive may be, for example, a two-component curable adhesive composed of a main agent and a curing agent, such as an epoxy resin adhesive, a silicone resin adhesive, and a polyurethane adhesive.
  • the adhesive may have no aromatic ring so that the resulting transparent laminate is not discolored by the irradiation of ultraviolet light.
  • the curing agent of the two-part reactive adhesive may be an aliphatic curing agent.
  • the adhesive layer in the transparent laminate of the present invention is prepared by dissolving the above-mentioned adhesive, for example, a main agent and a curing agent of a two-component curing adhesive, and a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber in a solvent. It can be obtained by curing a two-component UV curable adhesive composition.
  • the solvent may be, for example, ethyl acetate and the like.
  • the adhesive layer in the transparent laminate of the present invention has an adhesive layer amount of 2.0 g / m 2 or more as the amount of the adhesive layer per unit area of the transparent laminate, from the viewpoint of sufficiently increasing the lamination strength of the outer layer and the inner layer. .5g / m 2 or more, 3.0 g / m 2 or more, 3.5 g / m 2 or more, or 4.0 g / m 2 or more may be an amount.
  • the amount of the adhesive layer per unit area of the transparent laminate is 8.0 g / m 2 or less from the viewpoint of securing the laminate strength or enabling the production by the coating method, or both of them. , 7.0 g / m 2 or less, 6.0 g / m 2 or less, or 5.0 g / m 2 or less.
  • the benzotriazole-based ultraviolet absorber may be a hydroxyphenyl-substituted benzotriazole compound, a halide thereof or the like.
  • the hydroxyphenyl substituted benzotriazole compound is, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2- (2-hydroxy-5-methylphenyl) benzotriazole) 2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) benzotriazole, It may be 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole and the like.
  • the halide of the hydroxyphenyl substituted benzotriazole compound is, for example, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (alias: 2- (5-chloro-2H-benzo) Triazol-2-yl) -6-t-butyl-4-methylphenol), 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy) -3- (2-Methylpentan-2-yl) -5- (2-methylbutan-2-yl) phenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-t-butyl-5- ( It may be 2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole or the like.
  • the amount of the benzotriazole-based ultraviolet absorber in the adhesive layer, per area of the transparent laminate e.g., 0.10 g / m 2 or more, 0.13 g / m 2 or more, 0.15 g / m 2 or more, 0. 17 g / m 2 or more, 0.19 g / m 2 or more, or 0.21 g / m 2 or more.
  • the amount of the benzotriazole-based ultraviolet absorber used is sufficiently large, ultraviolet light can be effectively blocked, and in the wavelength region of 380 nm to 400 nm where blocking by the benzophenone-based ultraviolet absorber described below is insufficient. Ultraviolet light and ultraviolet light near a wavelength of 310 nm can be sufficiently blocked.
  • the amount of the benzotriazole-based ultraviolet absorber in the adhesive layer, per area of the transparent laminate e.g., 0.30 g / m 2 or less, 0.28 g / m 2 or less, 0.25 g / m 2 or less, 0. It may be 23 g / m 2 or less, or 0.21 g / m 2 or less.
  • the adhesive layer in which the amount of the benzotriazole-based ultraviolet absorber used is not excessive can laminate the outer layer and the inner layer with high adhesion, and the laminate strength between both layers can be made sufficiently high.
  • the amount of the benzotriazole-based UV absorber used in the adhesive layer is, for example, 0.13 g / m 2 or more per area of the transparent laminate, in consideration of the balance between UV blocking properties and laminate strength as much as possible. It may be in the range of .28 g / m 2 or less.
  • the benzophenone based ultraviolet absorber may be a hydroxy-substituted benzophenone compound or the like.
  • hydroxy-substituted benzophenone-based UV absorbers examples include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone (alias: [2 -Hydroxy-4- (octyloxy) phenyl] (phenyl) methanone), 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone , 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4'-dimethoxyphenyl, 2,2 ', may be 4,4'-tetrahydroxy benzophenone.
  • the amount of the benzophenone ultraviolet absorber in the adhesive layer, per area of the transparent laminate e.g., 0.10 g / m 2 or more, 0.13 g / m 2 or more, 0.15 g / m 2 or more, 0.17 g / M 2 or more, 0.18 g / m 2 or more, or 0.20 g / m 2 or more.
  • the amount of the benzophenone-based ultraviolet absorber used is sufficiently large, it is possible to sufficiently block ultraviolet light around a wavelength of 330 nm, in particular, for which blocking by the benzotriazole-based ultraviolet absorber is insufficient.
  • the adhesive layer in which the amount of the benzophenone-based ultraviolet absorber used is not excessive can laminate the outer layer and the inner layer with high adhesion, and the laminate strength between both layers can be made sufficiently high.
  • the amount of the benzophenone-based UV absorber used in the adhesive layer is, for example, 0.15 g / m 2 or more per area of the transparent laminate, in consideration of the balance between the UV blocking property and the laminate strength. It may be in the range of 76 g / m 2 or less.
  • the total amount of the benzotriazole-based ultraviolet absorber and the benzophenone-based ultraviolet absorber in the adhesive layer is, for example, 0.30 g / m 2 or more, 0.35 g / m 2 or more, per unit area of the transparent laminate. .40g / m 2 or more, or may be at 0.45 g / m 2 or more, e.g., 2.50 g / m 2 or less, 2.00 g / m 2 or less, 1.50 g / m 2 or less, 1.00 g / m 2 or less, or 0.50 g / m may be 2 or less.
  • the content of each of the benzotriazole-based ultraviolet absorber and the benzophenone-based ultraviolet absorber in the transparent laminate is obtained by immersing the transparent laminate sample in a solvent to extract the ultraviolet absorber and concentrating as necessary. It can quantify by measuring the liquid chromatography of the extracted liquid. The measurement results of liquid chromatography may be converted to values per unit area of the original transparent laminate sample.
  • an extraction solvent for example, chloroform is suitable.
  • the inner layer in the transparent laminate of the present invention may be a layer having a single layer structure or a multilayer structure including a transparent resin layer.
  • the inner layer may include a transparent resin layer having heat sealability, and an outer layer resin May contain a transparent resin layer having good heat sealability.
  • a transparent resin which comprises an inner layer polyethylene etc.
  • polyethylene etc. can be mentioned, for example, you may select suitably from LDPE, LLDPE, MDPE, HDPE etc., and may use.
  • the transparent resin constituting the inner layer may be a sheet of these resins, a film, or a coating film formed using a composition containing these resins, and in particular may be an LLDPE film.
  • the inner layer may be a single layer or multi-layer layer comprising an LLDPE film.
  • the inner layer in the transparent laminate of the present invention may have a base layer which imparts rigidity to the transparent laminate, in addition to the transparent resin layer as described above, particularly the LLDPE film.
  • the base material layer may be, for example, a polyester layer, a nylon layer or the like.
  • the polyester layer may be, for example, a uniaxial or biaxial stretched film composed of polyethylene terephthalate (PET) or the like.
  • PET polyethylene terephthalate
  • the nylon layer may be, for example, a uniaxial or biaxial stretched film made of 6-nylon, 6,6-nylon or the like.
  • the thickness of the base material layer may be, for example, 8 ⁇ m or more, 10 ⁇ m or more, or 12 ⁇ m or more.
  • the base layer has a thickness of, for example, 25 ⁇ m.
  • it may be 20 ⁇ m or less, or 15 ⁇ m or less.
  • the thickness of the inner layer may be, for example, 20 ⁇ m or more, 40 ⁇ m or more, 60 ⁇ m or more, or 80 ⁇ m or more, and for example, 400 ⁇ m or less, 350 ⁇ m or less, 300 ⁇ m or less, 250 ⁇ m or less, 200 ⁇ m or less, 150 ⁇ m or less, or 100 ⁇ m or less Good.
  • these thicknesses are values including the thickness of the substrate layer.
  • the transparent laminate of the present invention may optionally include a printing layer.
  • the print layer may include, for example, a print name such as a product name of the contents, an explanation, notes, and the like, and a design for stimulating purchase intention.
  • the printing layer may be disposed on either the outer layer or the inner layer. When the outer layer and the inner layer are multilayers, they may be disposed in any of these multilayers. For example, a printing layer may be disposed on the outermost surface of the inner layer opposite to the side in contact with the content, and the outer layer may be adhered onto the printing layer via the predetermined adhesive layer of the present invention, It is included in the scope of the present invention.
  • the formation of the printing layer may be performed using a known ink composition (for example, a UV ink composition) by an appropriate printing method such as offset printing, gravure printing, flexographic printing, letterpress printing, and the like.
  • a known ink composition for example, a UV ink composition
  • an appropriate printing method such as offset printing, gravure printing, flexographic printing, letterpress printing, and the like.
  • the transparent laminate of the present invention may be produced, for example, by a method comprising laminating an outer layer and an inner layer via an adhesive layer containing a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber.
  • the outer layer, the inner layer, and the ultraviolet light absorber desired ones may be selected and used from those exemplified above as the material constituting the transparent laminate.
  • the outer layer or the inner layer has a multilayer structure, for example, it may be used after being laminated by an appropriate method such as melt extrusion lamination or dry lamination.
  • the processed surface of the layer Prior to lamination in the case where the outer layer or the inner layer has another layer configuration, and adhesion between the outer layer and the inner layer, the processed surface of the layer may be subjected to an appropriate treatment such as corona discharge treatment in advance.
  • the adhesive layer may be formed, for example, on the outer layer or the inner layer or on both sides.
  • Adhesive, Benzotriazole type ultraviolet absorber and benzophenone type ultraviolet absorber After application of the UV-absorbing adhesive composition comprising ethyl acetate, the outer layer and the inner layer are laminated and then formed by removing the solvent in the UV-absorbing adhesive composition and curing the adhesive May be done.
  • the adhesive contained in the above-mentioned UV-absorbing adhesive composition may be a one-component adhesive or a two-component (two-component curing) adhesive, and the adhesive exemplified above Among the agents, desired ones may be selected and used.
  • the type and amount of each of the benzotriazole-based ultraviolet absorber and the benzophenone-based ultraviolet absorber may be appropriately set according to the desired adhesive layer in the transparent laminate.
  • the amount of ethyl acetate used is such that the solid content in the resulting UV-absorbing adhesive composition is, for example, 10% by weight or more, 15% by weight or more, or 20% by weight or more, for example, 60% by weight or less, 50% It may be used in an amount of less than 40% by weight.
  • the outer layer and the inner layer are laminated by dry lamination using a two-component curable UV-absorbing adhesive composition containing a two-component curable adhesive and a UV absorber.
  • the two-part curable UV-absorbing adhesive composition may contain a two-part curable adhesive, a benzotriazole-based UV absorber and a benzophenone-based UV absorber, and ethyl acetate.
  • the transparent laminate of the present invention is highly transparent, particularly highly transparent to visible light, and excellent in the blocking property to ultraviolet light.
  • the ultraviolet-visible / near-infrared spectrophotometer is used for the transparent laminate of the present invention, under the conditions of a measurement wavelength of 200 nm to 500 nm, a scanning speed of 600 nm / min, and a slit width of 4.00 nm.
  • the ultraviolet transmittance at wavelengths of 360 nm, 330 nm, and 270 nm may be 5.0% or less.
  • the ultraviolet light transmittance at 360 nm of the transparent laminate at this time may be 4.5% or less, 4.0% or less, 3.5% or less, or 3.0% or less.
  • the ultraviolet transmittance at 330 nm and 270 nm of the transparent laminate may be 4.0% or less, 3.0% or less, 2.0% or less, or 1.5% or less, respectively.
  • the transparent laminate of the present invention has a high blocking efficiency to ultraviolet light, particularly in the wavelength region of 360 nm or less. Therefore, the transparent laminate of the present invention is provided with a high degree of ultraviolet blocking properties even when the outer layer and the inner layer are materials (for example, PE) which do not have ultraviolet blocking properties.
  • PET generally used as a laminate material blocks ultraviolet light in a wavelength range of 300 nm or less well, but exhibits significant transmittance in a wavelength range of 320 nm or more. Since the transparent laminate of the present invention can effectively block ultraviolet light of 360 nm or less even when the outer layer and the inner layer are composed of PET, the ultraviolet light originally possessed by the material of the outer layer and the inner layer The blocking range will be expanded.
  • the haze of the transparent laminate of the present invention measured according to JIS K 7105 is, for example, 40% or less, 38% or less, 36% or less, 34% or less, 32% or less It may be 30% or less.
  • the laminate strength between both layers is very high.
  • the T-peel strength measured according to JIS K 6854 is 10.0 N / 15 mm or more, 12.0 N / 15 mm or more, It may be 13.0 N / 15 mm or more, 13.5 N / 15 mm or more, 14.0 N / 15 mm or more, 14.5 N / 15 mm or more, or 15 N / 15 mm or more.
  • the transparent laminate of the present invention may be used, for example, as a laminate tube container, a laminate packaging bag, and the like.
  • the transparent laminate of the present invention may be used, for example, as a laminated tube container for cosmetics, pharmaceuticals, food and the like.
  • the laminate tube container may comprise a body, a mouth smaller in diameter than the body, and a shoulder connecting the body and the mouth.
  • the laminated tube container is formed, for example, by rolling the transparent laminate of the present invention into a cylindrical shape to form a cylindrical body, and welding it to a separately manufactured shoulder and mouth, forming the shoulder by compression molding It may be manufactured by an appropriate method etc. including a method of simultaneously performing welding with the cylindrical body and the like.
  • the resin films and reagents used in the following examples and comparative examples are as follows.
  • the number in parentheses after the name of the resin film is the film thickness ( ⁇ m).
  • LLDPE 1 (100): manufactured by Tamapoly Co., Ltd., linear low density polyethylene, product name "SE620N”, thickness 100 ⁇ m
  • LLDPE 2 (80): manufactured by Toyobo Co., Ltd., linear low density polyethylene, product name “LIX-NP L4102”, thickness 80 ⁇ m LDPE: manufactured by Asahi Kasei Co., Ltd., low density polyethylene, product name "Suntec-LD M1880E” PET (12): Unitika Co., Ltd. product, biaxially stretched polyester film, product name "PETB”, thickness 12 ⁇ m
  • ester-based main agent made by Toyo Ink Co., Ltd., product name "TM277", non-volatile content 55% by weight
  • aliphatic curing agent made by Toyo Ink Co., Ltd., product name "CAT-RT86, non-volatile content 60% by weight
  • ⁇ UV absorber> LA-36: manufactured by ADEKA Co., Ltd., benzotriazole-based ultraviolet absorber, 2- (5-chloro-2H-benzotriazol-2-yl) -6-t-butyl-4-methylphenol, trade name “Adekastab LA- 36 " 1413: manufactured by ADEKA Co., Ltd., benzophenone-based ultraviolet absorber, [2-hydroxy-4- (octyloxy) phenyl] (phenyl) methanone, product name "Adecastab 1413"
  • UV Absorbent Adhesive Composition A solution A was obtained by mixing 10 g of an adhesive (main agent) (5.5 g of non volatile matter) and 11.94 g of ethyl acetate. A predetermined amount of each of the ultraviolet absorbers “LA-36” and “1413” was weighed and mixed with the solution A to obtain a solution B. Next, 2 g of an adhesive (hardening agent) (1.2 g of non-volatile components) was mixed with the solution B to prepare a two-component curable ultraviolet-absorbing adhesive composition.
  • an adhesive hardening agent
  • the UV absorbers “LA-36” and “1413” are each 100% by weight of the solid content in the adhesive (that is, the total weight of the adhesive (main agent) and the non-volatile components of the adhesive (hardener)). The amount which becomes the ratio (weight%) shown by the "weight ratio with respect to adhesive agent” column of Table 1 when mixing it as% was mixed and used.
  • the UV-absorbing adhesive composition is applied by gravure coating at a coating weight of 4.2 g / m 2 in terms of solid content on one corona discharge-treated surface of LLDPE 1 (100), and another one A transparent laminate of the following layer configuration was obtained by bonding to the corona discharge treated surface of LLDPE 1 (100) and leaving it to stand at 40 ° C. for 5 days (120 hours) to cure the adhesive.
  • the obtained transparent laminate was cut into a square sheet of 10 cm ⁇ 10 cm to obtain a sample. This sheet was cut into substantially square pieces of about 1 cm on a side, and immersed in chloroform to extract the ultraviolet absorber. The extract was concentrated under reduced pressure and then subjected to liquid chromatography to quantify the amount of the ultraviolet absorber contained in the extract, and converted to a value per unit area of the transparent laminate sample used for the measurement.
  • UV transmittance of the transparent laminate sample obtained under the following conditions was measured using an ultraviolet-visible near-infrared spectrophotometer, product name "UH4150” manufactured by Hitachi High-Tech Science Co., Ltd. It was measured. At this time, ultraviolet ray transmittances at wavelengths of 360 nm, 330 nm, and 270 nm were adopted as an indicator of the transparency of the transparent laminate. Measurement wavelength: 200 nm to 500 nm Scanning speed: 600 nm / min Sampling interval: 1 nm Slit width: 4.00 nm
  • FIG. 2 shows ultraviolet ray transmittance charts of transparent laminate samples of Comparative Examples 1 to 3 used as grounds for ultraviolet ray transmittances of wavelengths 360 nm, 330 nm, and 270 nm
  • FIG. The ultraviolet transmittance chart is shown in FIG. Although the UV transmittance charts of Examples 1 to 4 and 6 to 8 are omitted, the UV transmittance values in these Examples in Table 1 are the values extracted from the corresponding UV transmittance charts. It is.
  • the ultraviolet transmittance sharply decreases at a wavelength shorter than 400 nm, and it is around 360 nm In this case, the transmissivity level was reached without any problem, but peaks with high transmissivity were observed near wavelengths of 330 nm and 270 nm.
  • Comparative example in which the amount of the benzotriazole-based ultraviolet light absorber “LA-36” is increased to 7% by weight (corresponding to 0.34 g / m 2 per unit area of the transparent laminate) with respect to the nonvolatile matter in the adhesive composition In No. 4, as described above, the UV absorber in the adhesive composition could not be completely dissolved in the solvent.
  • the high ultraviolet transmittance was maintained up to around 380 nm.
  • the ultraviolet transmittance of the transparent laminate sample of Comparative Example 2 decreased at a wavelength lower than 380 nm, but maintained a high level near 360 nm, and a peak with high transmittance near 310 nm and 270 nm was observed. It was done.
  • the ultraviolet light transmittance of the transparent laminate sample of Comparative Example 3 in which the content of the benzophenone series ultraviolet light absorber “1413” in Comparative Example 2 was increased was generally decreased in the wavelength range shorter than 380 nm, but it was around 360 nm The level of transmittance was still high, and peaks with high transmittance around 310 nm and 270 nm were also maintained.
  • the transparent laminate sample of Example 1 containing both benzotriazole-based ultraviolet absorber “LA-36” and benzophenone-based ultraviolet absorber “1413” as the ultraviolet absorber in the adhesive layer has a thickness of 400 nm.
  • the ultraviolet transmittance sharply decreased at a shorter wavelength and reached a satisfactory transmittance level near 360 nm, and no rising peaks of transmittance near wavelengths 330 nm and 310 nm were observed. Although a peak at which the ultraviolet light transmittance slightly increases is confirmed around the wavelength of 270 nm, it is not a level that causes a problem.
  • the ultraviolet transmittances at the wavelengths of 360 nm, 330 nm, and 270 nm measured for the transparent laminate samples of Examples 2 to 8 all show low values.
  • the embodiment of the present invention which includes both the benzotriazole-based ultraviolet absorber and the benzophenone-based ultraviolet absorber in the adhesive layer exhibits high transparency to visible light while having a wavelength shorter than 360 nm. It has been verified that the UV radiation in the region can be absorbed and the UV transmission in the region measured in this example can be reduced to a problem-free level.
  • LLDPE1 (100) is laminated on the corona discharge treated surface of this PET (12) via a two-component reaction curing type dry laminating adhesive layer, and laminate A (PET (12) / adhesive layer / LLDPE1 (100) ))) Got.
  • Another LLDPE 1 (100) is laminated via the melted LDPE on the LLDPE 1 (100) side of the laminate A, and a laminate B (PET (12) / adhesive layer / LLDPE 1 (100) / LDPE (70) / LLDPE1 (100) was obtained.
  • a fused LDPE is laminated via the anchor coat layer on the PET (12) side of the laminate B to form a 40 ⁇ m thick LPDE layer (LDPE (40)), the laminate C (LDPE (40)) / PET (12) / adhesive layer / LLDPE1 (100) / LDPE (70) / LLDPE1 (100)) was obtained.
  • UV-absorbing adhesive composition is gravure-coated onto the surface of the base laminate on the LDPE (40) side having a printed pattern by conversion of a solid content of 4.2 g / m 2 . It apply
  • UV absorber contained in the produced transparent laminate is quantified by liquid chromatography in the same manner as in [Comparative Examples 1 to 4 and Examples 1 to 8]. did.
  • FIG. 4 The chart of the ultraviolet ray transmittance thus obtained is shown in FIG. 4 and FIG. Fig.4 (a) is an ultraviolet-ray transmittance chart before wiping off the surface of the transparent laminated body obtained in Example 13 by ethanol, FIG.4 (b) wiped off the surface of this transparent laminated body with ethanol It is a ultraviolet ray transmittance chart after.
  • Fig.5 (a) is an ultraviolet-ray transmittance chart before wiping off the back surface of the transparent laminated body obtained in Example 13 by ethanol, FIG.5 (b) wiped the back surface of this transparent laminated body with ethanol It is a ultraviolet ray transmittance chart after.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Packages (AREA)
  • Wrappers (AREA)
  • Adhesive Tapes (AREA)
PCT/JP2018/031218 2017-10-10 2018-08-23 透明積層体 WO2019073702A1 (ja)

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SG11202001496RA SG11202001496RA (en) 2017-10-10 2018-08-23 Transparent laminate
MYPI2020001000A MY194442A (en) 2017-10-10 2018-08-23 Transparent laminate

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JP2017196719A JP6797095B2 (ja) 2017-10-10 2017-10-10 透明積層体

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JP2021178446A (ja) * 2020-05-12 2021-11-18 共同印刷株式会社 ラミネートチューブ用積層体

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JP7387330B2 (ja) * 2019-08-09 2023-11-28 東和薬品株式会社 ボルテゾミブ保存用容器
JP2022022706A (ja) * 2020-07-02 2022-02-07 株式会社サンエー化研 包装用フィルム及び包装袋

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JPH10279901A (ja) * 1997-02-04 1998-10-20 Oji Paper Co Ltd 粘着シートおよび粘着シートの製造方法
JPH11116910A (ja) * 1997-10-15 1999-04-27 Sekisui Chem Co Ltd 粘着シート
JP2000123621A (ja) * 1998-10-13 2000-04-28 Otsuka Chem Co Ltd 蛍光灯被覆材
JP2004315549A (ja) * 2003-04-10 2004-11-11 Mikado Kako Kk 粘着テープ及びその製造方法
JP2011093958A (ja) * 2009-10-27 2011-05-12 Toray Advanced Film Co Ltd 近赤外線吸収性粘着剤組成物および近赤外線吸収性粘着剤層
WO2013147101A1 (ja) * 2012-03-30 2013-10-03 リンテック株式会社 自動車ホイール保護用粘着フィルム
JP2015229759A (ja) * 2014-06-06 2015-12-21 日東電工株式会社 光学用粘着シート

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JPH10279901A (ja) * 1997-02-04 1998-10-20 Oji Paper Co Ltd 粘着シートおよび粘着シートの製造方法
JPH11116910A (ja) * 1997-10-15 1999-04-27 Sekisui Chem Co Ltd 粘着シート
JP2000123621A (ja) * 1998-10-13 2000-04-28 Otsuka Chem Co Ltd 蛍光灯被覆材
JP2004315549A (ja) * 2003-04-10 2004-11-11 Mikado Kako Kk 粘着テープ及びその製造方法
JP2011093958A (ja) * 2009-10-27 2011-05-12 Toray Advanced Film Co Ltd 近赤外線吸収性粘着剤組成物および近赤外線吸収性粘着剤層
WO2013147101A1 (ja) * 2012-03-30 2013-10-03 リンテック株式会社 自動車ホイール保護用粘着フィルム
JP2015229759A (ja) * 2014-06-06 2015-12-21 日東電工株式会社 光学用粘着シート

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Publication number Priority date Publication date Assignee Title
JP2021178446A (ja) * 2020-05-12 2021-11-18 共同印刷株式会社 ラミネートチューブ用積層体
JP7482679B2 (ja) 2020-05-12 2024-05-14 共同印刷株式会社 ラミネートチューブ用積層体

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MY194442A (en) 2022-11-30
JP2019069552A (ja) 2019-05-09
SG11202001496RA (en) 2020-03-30

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