JP2006305833A - Manufacturing method of laminated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain desired adhesive strength while reducing bubbles involved in the gap between base materials at the time of lamination. <P>SOLUTION: In the manufacturing method of a laminated product, a lamination aid, which comprises a compound absorbed in the laminating surface of at least one base material and having a viscosity of 1,000 mPa s or below at 25°C, is interposed between the laminating surfaces of the base materials when the film-like or sheetlike base material and the separate film-like or sheetlike base material are laminated. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a laminated product using a laminating aid.

  In recent years, various plastic films and sheets, metal-deposited plastic films, metal foils, metal strips, etc. are laminated as packaging materials and industrial materials for foods, pharmaceuticals, detergents, etc., and laminate products that take advantage of the characteristics of each material Is often used.

As a method for producing such a laminate product, a method through an adhesive layer and a method of heat-sealing a film are known. For example, a method in which a pressure-sensitive adhesive is applied to a laminate surface of a substrate and laminated (Japanese Patent Laid-Open No. 2003-003145), or a substrate whose laminate surface is a self-bonding plastic film layer is heated or heated / pressurized. A method of fusing (Japanese Patent Laid-Open No. 11-165372) is known. In any of the above methods, when laminating, particularly when laminating is performed continuously using a roll laminator, bubbles are involved between the substrates, and the resulting laminate product has a low quality in which bubbles are present. In addition, there is a problem that tearing or peeling due to foaming occurs depending on the conditions of subsequent processing steps.
JP 2003-3145 A Japanese Unexamined Patent Publication No. 11-165372

  This invention is made | formed in view of this situation, and provides the manufacturing method of the laminated product which obtains desired adhesive strength and reduces the bubble caught between base materials at the time of lamination.

  The present invention relates to the following.

  1. When laminating a film or sheet substrate with another film or sheet substrate, it can be absorbed by the laminate surface of at least one substrate and has a viscosity at 25 ° C. of 1,000 mPa · s or less. A method for producing a laminated product, characterized in that a laminating aid comprising a compound is interposed on a laminating surface of a substrate.

  2. 2. The method for producing a laminated product according to 1 above, wherein a laminating aid is applied to or sprayed on the laminating surface to intervene on the laminating surface of the substrate.

  3. 3. The method for producing a laminated product according to 1 or 2 above, wherein the laminating surface of the substrate on which the laminating aid can be absorbed is a layer containing a resin.

  4). 4. The method for producing a laminated product as described in 3 above, wherein the resin-containing layer is a layer comprising a curable resin composition.

  5. 5. The method for producing a laminated product as described in 4 above, wherein the curable resin composition is heat curable or electromagnetic radiation curable.

  6). The method for producing a laminated product according to any one of 4 to 5, wherein the curable resin composition contains an acrylic resin or a polyester resin.

  7). The method for producing a laminated product according to any one of 1 to 6 above, wherein the laminating aid is compatible with the laminate surface of the substrate on which the laminating aid can be absorbed.

  8). The method for producing a laminated product according to any one of 1 to 7, wherein the laminating aid is a monomer having a vinyl bond or an oligomer thereof.

  9. The method for producing a laminated product according to any one of 1 to 8 above, wherein the laminating aid is acrylic acid or methacrylic acid or a derivative thereof, a styrenic monomer, or an oligomer thereof.

  The manufacturing method of the laminate product of the present invention can obtain a desired adhesive strength and reduce air bubbles that are caught between the substrates during lamination. In addition, the method for producing a laminate product of the present invention does not necessarily require a third layer for strengthening the adhesion between substrates, and can be laminated under mild conditions to deteriorate or deform the substrate. Laminated products can be manufactured without any problems.

  An example of the manufacturing method of the laminate product of this invention is demonstrated using drawing. FIG. 1 is a conceptual diagram showing an example of a method for producing a laminate product of the present invention, and relates to a method using a roll laminator. The laminating aid 3 is applied to the laminating surface of the film-like or sheet-like substrate 2 by the coating roll 4, and the laminating surface of the substrate 2 and the laminating surface of the film-like or sheet-like substrate 1 are laminated by the laminating roll 5. The laminate product 6 is manufactured. In this example, the laminating aid 3 is applied only to the laminating surface of the base material 2, but the coating roll 4 is also provided on the base material 1 side, and the laminating aid 3 is also applied to the laminating surface of the base material 1. I do not care. Further, a laminating aid may be applied to the laminating surface of the base material immediately before the base materials 1 and 2 are laminated.

  The film-like or sheet-like substrate in the present invention may be a plastic film or sheet, a metal-deposited plastic film, a metal foil, a metal strip, or the like, or may be a multilayered product thereof. Further, a pressure-sensitive adhesive, paint, or the like may be applied to the non-laminate surface. The thickness of the substrate is appropriately selected and is usually 3 to 500 μm.

  The laminate surface of at least one film-like or sheet-like substrate must be capable of absorbing the laminating aid. For this purpose, a film-like or sheet-like base material itself has a property capable of absorbing the laminating aid, or a multilayer base formed by providing a layer capable of absorbing the laminating aid on the laminating surface of the base material. It is necessary to be a material. This is particularly necessary when using a metal foil or metal strip as the substrate.

  In order for the laminate surface of the base material to absorb the laminating aid, the laminating surface is preferably compatible with the laminating aid.

The at least one film-like or sheet-like substrate itself is, for example, a vinyl resin such as polyethylene, polypropylene, polyethylene-polypropylene blend polymer polyamide polyvinyl chloride vinyl alcohol, ethylene-vinyl alcohol; polyethylene terephthalate, polybutylene terephthalate, Polyester resins such as polyethylene naphthalate and polybutylene naphthalate; polycarbonate resins; acrylic resins such as butyl acrylate, ethyl acrylate, and butyl methacrylate; acrylic resins that are copolymers of methacrylic esters; isoprene, etc. Natural rubber resin; styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, styrene-ethylene-butadiene copolymer Rubber, synthetic rubber resin polyisobutylene and the like; and is formed of resin such as a mixture of these resins, among others, acrylic resins are preferred. Such a resin may be a single layer film or a multilayer film.
In addition, at least one of the film-like or sheet-like base materials may have a laminate surface on which a layer capable of absorbing a laminating aid is laminated. It is preferable that it is a layer containing. As such a resin, the resins described above and resins generally known as materials such as adhesives, pressure-sensitive adhesives and paints can be used, and those having a high molecular weight and those having a relatively low molecular weight can be used. For example, a saturated polyester, an unsaturated polyester, an acrylic resin with or without a polymerizable functional group (acrylic acid or methacrylic acid or a polymer or copolymer of derivatives thereof, which includes acrylic acid or methacrylic acid or Including copolymers of these derivatives and other unsaturated monomers), styrene resins (polystyrene, copolymers of styrene and acrylonitrile, acrylic acid or methacrylic acid, or other monomers such as these derivatives) Etc.), and amino resins such as polyurethane resins and melamine resins.

  Moreover, as a layer containing said resin, a curable resin composition is preferable.

  The curable resin composition contains a reactive compound, and for example, one that cures by heat, one that cures by irradiation with electromagnetic radiation, or one that cures by irradiation with heat and electromagnetic radiation is preferable. As electromagnetic rays, ultraviolet rays, electron beams, infrared rays, and the like are used.

  The curable resin composition is particularly preferably a composition that initiates polymerization with a polymerization initiator, that is, a composition that includes a compound having a polymerization initiator and a reactive functional group. Here, examples of the compound having a reactive functional group include a resin having a polymerizable functional group, an oligomer having a polymerizable functional group, a monomer having a polymerizable functional group, and the like, and a monomer having a polymerizable functional group. When the body is used, it is preferable to use a resin having a polymerizable functional group or an oligomer having a polymerizable functional group.

  Examples of the resin having a polymerizable functional group include an acrylic resin having a polymerizable functional group and an unsaturated polyester, and the resin having no polymerizable functional group includes an acrylic resin having no polymerizable functional group, a saturated polyester, and the like. There is.

  Examples of the monomer having a polymerizable functional group include acrylic acid, methacrylic acid, and derivatives thereof (hereinafter referred to as “acrylic acid derivatives”).

  Examples of acrylic derivatives other than acrylic acid and methacrylic acid include acrylic acid or methacrylic acid derivatives. Specifically, monomers having one polymerizable unsaturated bond in the molecule include methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, n-octyl methacrylate, and lauryl methacrylate. , Alkyl methacrylates such as stearyl methacrylate, methyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, alkyl acrylates such as n-octyl acrylate, aralkyl methacrylates such as benzyl methacrylate, benzyl acrylate, etc. Alkoxyalkyl methacrylates such as aralkyl acrylate and butoxyethyl methacrylate, butoxyethyl acrylate Alkoxyalkyl acrylates such as N, N-dimethylaminoethyl methacrylate, aminoalkyl methacrylates such as N, N-dimethylaminoethyl acrylate, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, methacrylate esters of (diethylene glycol ethyl ether), (triethylene glycol butyl ether) ) Methacrylic acid ester, (dipropylene glycol methyl ether) methacrylic acid ester, etc. (polyalkylene glycol alkyl ether) methacrylic acid ester, (diethylene glycol ethyl ether) acrylic acid ester, (triethylene glycol butyl ether) acrylic acid Esters (polyalkylene glycol alkyls such as acrylic acid esters of (dipropylene glycol methyl ether)) (Polyalkylene glycol aryl) such as (polyether glycol aryl ether), methacrylic acid ester of (polyalkylene glycol aryl ether) such as methacrylic acid ester of (hexaethylene glycol pheny ether), acrylic acid ester of (hexaethylene glycol pheny ether) Ether) acrylic acid esters, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclodecatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate, etc. Methacrylic acid ester or acrylic acid ester having an alicyclic group, heptadecafluorodecyl methacrylate Fluorinated alkyl methacrylates such as heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4 -Methacrylic acid ester or acrylic acid ester having a hydroxyl group such as hydroxybutyl acrylate, glycerol methacrylate or glycerol acrylate, methacrylic acid ester or acrylic acid ester having a carboxyl group such as acrylic acid or methacrylic acid, glycidyl such as glycidyl methacrylate or glycidyl acrylate Methacrylic acid ester or acrylic acid ester having a group, acrylamide, etc. That. These can be used alone or in combination of two or more.

  As an acrylic acid derivative, in addition to the monomer having one polymerizable unsaturated bond in the molecule, a monomer or oligomer having two or more polymerizable unsaturated bonds in the molecule can be used. Such monomers include bisphenol A dimethacrylate 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol. Dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pen Tame Acrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, Tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, bisphenol A alkylene Diacrylate of xoxide adduct, epichlorohydrin modified product of bisphenol A and addition ester of acrylic acid, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol di Methacrylate, neopentyl glycol diacrylate, diacrylate of alkylene oxide adduct of phosphoric acid, epichlorine modification of phthalic acid and addition ester of acrylic acid, diacrylate of polyethylene glycol, dimethacrylate of polypropylene glycol, tetraethylene glycol diacrylate 1,6-Hexanediol epichlorine modified product and acrylic acid addition esterified product (has two aquilyl groups in one molecule) ), Trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylate of alkyne oxide adduct of phosphoric acid, triacrylate of alkylene oxide adduct of trimethylolpropane, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetra Examples include acrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. These monomers can be used alone or in combination of two or more.

  As a monomer having a polymerizable functional group, a monomer having one polymerizable unsaturated bond such as acrylonitrile, styrene, vinyl acetate, ethylene, propylene, etc. in the molecule in addition to the above acrylic acid derivatives is used. Can do. In addition, monomers other than the acrylic acid derivatives described above and having two or more polymerizable unsaturated bonds in the molecule (such as divinylbenzene) can also be used.

  Examples of the oligomer having a polymerizable functional group include a urethane oligomer having an unsaturated polymerizable functional group. Such a urethane oligomer can be produced by reacting a compound having an isocyanate group obtained by reacting a polyhydric alcohol compound and a polyvalent isocyanate compound with a compound having a hydroxyl group and a reactive double bond. it can.

  Examples of polyhydric alcohols include propylene glycol, tetramethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-methyl- 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, poly1,2-butylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol-propylene glycol block copolymer, Ethylene glycol-tetramethylene glycol copolymer, methylpentanediol modified polytetramethylene glycol, propylene glycol modified polytetramethylene glycol, propylene oxide adduct of bisphenol A There are propylene oxide adducts of hydrogenated bisphenol A, propylene oxide adducts of bisphenol F, propylene oxide adducts of hydrogenated bisphenol F, etc. Polyisocyanate compounds include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexa Diisocyanates such as methylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornene diisocyanate, and the above Diisocyanate polymer or diisocyanate urea Sex body, there is a biuret modified product, or the like.

  Examples of the compound having a hydroxyl group and a reactive double bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, ethylene glycol -Propylene glycol block copolymer monoacrylate, ethylene glycol-tetramethylene glycol copolymer monoacrylate, caprolactone-modified monoacrylate (trade name Plaxel FA series, manufactured by Daicel Chemical Industries), acrylic acid derivatives such as pentaerythritol triacrylate, 2-hydroxyethyl Methylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate 4-hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ethylene glycol-propylene glycol block copolymer monomethacrylate, ethylene glycol-tetramethylene glycol copolymer monomethacrylate, caprolactone modified monomethacrylate ( Trade name Plaxel FM series: manufactured by Daicel Chemical Industries, Ltd.) and methacrylic acid derivatives such as pentaerythritol trimethacrylate.

  The monomer or oligomer having two or more polymerizable unsaturated bonds in the molecule is preferably used together with the monomer having one polymerizable unsaturated bond in the molecule.

  As the polymerization initiator, a photopolymerization initiator can be used, and it can be selected from known materials such as benzophenone, anthraquinone, benzoin, sulfonium salt, diazonium salt, onium salt and the like.

  More specifically, as a photopolymerization initiator, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Aromatic ketone compounds such as anthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone Benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin ether compounds such as benzoin phenyl ether, benzyl, 2,2-diethoxyacetophenone, benzyldimethyl ketal, β- ( Acridine-9-yl) acrylic acid diester compounds, 9-phenylacridine, 9-pyridylacridine, acridine compounds such as 1,7-diacridinoheptane, 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxy Enyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer 2,4,5-tria such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer Reel imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propane etc.

  A thermal polymerization initiator may be used as the polymerization initiator. The thermal polymerization initiator is an initiator that generates radicals by heat, and specifically includes benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl. Peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl Examples thereof include organic peroxides such as peroxide and diacetyl peroxide. Also, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonyl). 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) ), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane].

  15 to 89.9 parts by weight of a monomer having a polymerizable functional group is used for 10 to 80 parts by weight of a resin having or not having a polymerizable functional group or 10 to 80 parts by weight of an oligomer having a polymerizable functional group. It is preferable to be used so that 0.1 to 5 parts by weight and 100 parts by weight as a whole.

  The above-described method for producing a multilayer film-like or sheet-like substrate is a method of laminating the resin on a substrate by coextrusion, a method of laminating the resin film or sheet on a substrate with an adhesive, and a necessity. In general, a method of adjusting the viscosity of the resin or the curable resin composition with an organic solvent and laminating the resin or the curable resin composition on a substrate by means of coating or the like is not limited thereto.

  The laminating aid can be absorbed by the laminating surface of the film-like or sheet-like substrate. That is, the laminating aid can be absorbed by the material forming the laminate surface and is preferably compatible with the material. Here, having compatibility means that the material for forming the laminate surface of the base material and the laminating aid are mixed and can be apparently integrated, and a mixed interface, that is, a single phase of the laminating aid is not formed. . When a laminating aid that does not have compatibility is used, a phase composed of the laminating aid alone is formed, and a third phase is interposed on the laminate surface of the base material, thereby achieving the object of the present invention. It may not be possible. Such a laminating aid is appropriately selected in combination with a material that forms a laminate surface of a film-like or sheet-like substrate. Examples include, but are not limited to, acrylic monomers, acrylic oligomers, urethane oligomers, and mixtures thereof among the monomers and oligomers described above.

  The laminating aid used in the present invention comprises a compound having a viscosity at 25 ° C. of 1,000 mPa · s or less, preferably 0.1 to 900 mPa · s, particularly preferably 0.1 to 800 mPa · s. When the viscosity exceeds 1,000 mPa · s, there is a problem that bubbles are easily caught between the substrates during lamination. The viscosity here is measured with an E-type viscometer manufactured by Brookfield.

  The molecular weight of the laminating aid is preferably 10,000 or less, more preferably 100 to 8000. When the molecular weight exceeds 10,000, the viscosity increases, and air bubbles may be easily caught between the substrates during lamination.

  The laminating aid is preferably a reactive compound, and is preferably one that is cured by heating or by irradiation with electromagnetic rays such as ultraviolet rays, electron beams, and infrared rays during or after laminating.

In the present invention, the laminating aid is preferably present at 0.1 to 5 g / m ^{2 and} more preferably 0.2 to 3 g / m ² on the laminate surface of the substrate. When the laminating aid becomes a continuous film or a substantially continuous film, it is supplied and interposed so that the thickness is preferably 0.1 to 5 μm, particularly preferably 0.2 to 3 μm. . The supply method is not particularly limited, but it is preferably carried out by applying or spraying a laminating aid on the laminating surface. For example, a method of applying using a coating roll as described above, or a method of spraying a laminating aid on the laminating surface can be mentioned. The timing for supplying the laminating aid to the laminating surface is not particularly limited and is appropriately selected depending on the supplying method, but is usually before or simultaneously with the laminating. When supplying the laminating aid before laminating, it is preferable to supply by laminating or spraying on the laminating surface of the substrate different from the substrate having the laminating surface capable of absorbing the laminating aid. Is preferably supplied by spraying between the laminate surfaces of both substrates. At the time of application or spraying, the laminating aid may be appropriately dissolved in a solvent and used, and in that case, it is dried after application as necessary. The amount of application or spraying of the laminating aid can be adjusted by controlling the number of rotations of the roll and the viscosity of the laminating aid. As the coating roll, a mirror surface roll, a gravure embossing roll, a sponge roll or the like is used, but is not limited thereto.

In the present invention, at least one of the film-like or sheet-like base material is one in which the laminate surface absorbs the laminating aid, but the other is preferably one in which the laminating surface does not absorb the laminating aid. In addition, the laminate surface is preferably not compatible with the laminating aid in the above-described sense. When the laminating aid is applied or sprayed on the laminating surface, the applied film does not necessarily need to be a uniform and continuous film, and may be discontinuous and evenly dispersed. Or when laminating a sheet-like base material, it is preferable that a puddle of laminating aid can be formed at those contact points. Referring to the drawings, when laminating film- or sheet-like substrates 1 and 2 with laminating roll 5, it is preferable that a puddle of laminating aid can be formed in the portion where both substrates are in contact. It is further preferable that this liquid pool is not interrupted in the axial direction of the roll.
A method of laminating a film-like or sheet-like substrate and another film-like or sheet-like substrate is generally a method using a roll laminator, but is not limited thereto. Lamination is preferably performed under heating or irradiation with electromagnetic rays such as ultraviolet rays, electron beams and infrared rays. The heating temperature is appropriately selected depending on the material and thickness of the film- or sheet-like substrates 1 and 2, the material of the laminated surface, and the like, but is usually 10 to 50 ° C. In addition, the atmosphere may be normal pressure, pressurized or reduced pressure, and is usually performed under 0.001 to 0.8 MPa.

  When the laminate product of the present invention is laminated with a layer capable of absorbing the above-mentioned laminating aid, by peeling off one of the film-like or sheet-like base materials, a decorative film or sheet, for surface protection It can be used as an adhesive or adhesive film or an adhesive or adhesive sheet. For the peelability of one substrate, the material may be selected in consideration of the adhesion between the layer that can absorb the laminating aid (absorbing the laminating aid) and the film, but in general, polypropylene, polyethylene, etc. The polyolefin is preferred.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by these Examples.

Example 1
Acrylic resin BR-77 (product name of Mitsubishi Rayon Co., Ltd.) having unsaturated polymerizable functional groups as an ultraviolet curable coating on one side of a polypropylene film (manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 40 μm, unsaturated polymerization Urethane oligomer EB8804 (product name of Daicel UCP Co., Ltd.) and photopolymerization initiator IR # 819 (product name of Ciba Specialty Chemicals Co., Ltd.) (weight ratio 49.4 / 49.4 / 1) .2) was dissolved in a toluene / ethyl acetate mixed solution (weight ratio 50/50) so as to have a solid content of 47%, and applied to a coating amount of 50 μm and dried to obtain a film 1.

On one side of a polypropylene film having a thickness of 40 μm (manufactured by Hitachi Chemical Co., Ltd.), ethyl methacrylate (molecular weight 11 4, viscosity 0.65 mPa · s at 25 ° C.) as a coating aid is 2 μm (about 2 g / m ² ). The film 2 was obtained by coating with a coating roll.

  The acrylic resin surface of film 1 and the laminating aid coating surface of film 2 were combined and laminated using a roll laminator at a pressure of 0.5 MPa and a temperature of 50 ° C. A small pool of laminating aid was formed at the point where film 1 and film 2 were in contact with each other without interruption in the axial direction of the roll.

  The adhesive strength of the obtained laminate product was measured. The adhesive strength was measured by measuring the strength when peeling the film at a peeling angle of 90 degrees and a peeling speed of 200 mm / min using a Tensilon universal testing machine RT-100 manufactured by Orientec Co., Ltd. The peeled film was film 2 to which a laminating aid was applied.

  The presence or absence of delamination when heated at 80 ° C. for 1 hour was visually observed. The results are shown in Table 1.

  The laminate product obtained in this example was one that could be used as a decorative film by peeling off one film (film 2).

(Example 2)
A laminate product was obtained in the same manner as in Example 1 except that pentaerythritol triacrylate (molecular weight 298, viscosity at 730 mPa · s, product name of Shin-Nakamura Chemical Co., Ltd.) was used instead of ethyl methacrylate as a laminating aid. Similarly, the adhesive strength and the presence or absence of delamination were examined. The results are shown in Table 1.

  The laminate product obtained in this example was one that could be used as a decorative film by peeling off one film (film 2).

(Example 3)
As film 1 in Example 1, SK Dyne 1499 (product name of Soken Chemical Co., Ltd.) was added to one side of a polypropylene film having a thickness of 40 μm (manufactured by Hitachi Chemical Co., Ltd.) so that the solid content was 25% by weight. A laminate product was obtained in the same manner as in Example 1 except that the diluted product was applied and dried so that the coating amount was 20 μm, and the adhesive strength and the presence or absence of delamination were similarly examined. The results are shown in Table 1.

  The laminate product obtained in this example was one that could be used as a decorative film by peeling off one film (film 2).

(Comparative Example 1)
A laminate product was obtained in the same manner as in Example 1 except that dipentaerythritol hexaacrylate (molecular weight: 578, viscosity: 6600 mPa · s at 25 ° C.) was used in place of ethyl methacrylate as a laminating aid. The presence or absence of peeling was examined. The results are shown in Table 1.

(Comparative Example 2)
The same procedure as in Example 1 was conducted except that urethane oligomer UP-340P (molecular weight 13,000, viscosity at 25 ° C., 13,000 mPa · s, product name of Shin-Nakamura Chemical Co., Ltd.) was used instead of ethyl methacrylate as a laminating aid. A laminate product was obtained, and the presence of adhesive strength and delamination was similarly examined. The results are shown in Table 1.

  Examples 1 to 3 had high adhesive strength and were good in that foaming and delamination were not observed even at 80 ° C. heat treatment. On the other hand, Comparative Examples 1 and 2 had low adhesive strength, and foaming and delamination due to air bubbles involved during lamination were observed.

It is a conceptual diagram which shows an example of the lamination method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Film-like or sheet-like base material 2 Film-like or sheet-like base material 3 Lamination aid 4 Coating roll 5 Lamination roll 6 Laminated product

Claims (9)

  When laminating a film or sheet substrate with another film or sheet substrate, it can be absorbed by the laminate surface of at least one substrate and has a viscosity at 25 ° C. of 1,000 mPa · s or less. A method for producing a laminated product, characterized in that a laminating aid comprising a compound is interposed on a laminating surface of a substrate.   The method for producing a laminated product according to claim 1, wherein the laminating aid is applied to or sprayed on the laminating surface to intervene on the laminating surface of the substrate.   The method for producing a laminated product according to claim 1 or 2, wherein the laminating surface of the substrate capable of absorbing the laminating aid is a layer containing a resin.   The method for producing a laminated product according to claim 3, wherein the resin-containing layer is a layer made of a curable resin composition.   The method for producing a laminate product according to claim 4, wherein the curable resin composition is heat curable or electromagnetic radiation curable.   The method for producing a laminated product according to any one of claims 4 to 5, wherein the curable resin composition contains an acrylic resin or a polyester resin.   The method for producing a laminated product according to any one of claims 1 to 6, wherein the laminating aid is compatible with the laminate surface of the substrate on which the laminating aid can be absorbed.   The method for producing a laminated product according to any one of claims 1 to 7, wherein the laminating aid is a monomer having a vinyl bond or an oligomer thereof.   The method for producing a laminated product according to any one of claims 1 to 8, wherein the laminating aid is acrylic acid or methacrylic acid or a derivative thereof, a styrene monomer, or an oligomer thereof.

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