JP2016215392A - Set of sheet body and over-sheet, and method for producing design shee using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a set of a sheet body and an over-sheet body used for producing a design sheet having high adhesion to the body to be adhered, and, upon release removal, capable of being easily peel-removed without causing paste remaining upon peel removal.SOLUTION: Provided is a set of a sheet body and an over-sheet body used for producing a design sheet by piling a sheet body and an over-sheet body. The sheet body includes a peel film, an adhesive layer and a base material for a sheet body in this order, and the ober-sheet body includes a receiving layer and a base material for an over-sheet body, and the adhesive layer includes an acrylic polymer, an active ray polymerizable oligomer, a polymerization initiator and a cross-linking agent.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a set of a sheet body and an oversheet body and a method for producing a design sheet using the set.

  In shopping malls and the like, sheets on which various images and contents of events are written are attached to adherends such as floor walls according to seasons and events.

  These sheets are required to have a high adhesive strength that does not peel off the adherend during an event or the like. On the other hand, it has been required that the adherend can be easily peeled off and removed from the adherend at the turn of the season or after the end of the event.

  By the way, as a pressure-sensitive adhesive composition for use in a pressure-sensitive adhesive tape or the like used in a manufacturing process of an electronic component, JP 2012-12506 A discloses an acrylic polymer, an energy beam polymerizable oligomer, and a polymerization initiator. And an energy ray easily peelable pressure-sensitive adhesive composition containing a crosslinking agent.

JP 2012-12506 A

  The present invention has been made in view of the above problems, and has a high adhesive force to an adherend, and can be easily peeled and removed without causing adhesive residue when peeling and removing. It is to provide a set of a sheet body and an oversheet body, which is used for producing a sheet.

According to the present invention, the sheet body and the oversheet body are overlapped to be used for producing a design sheet, a set of the sheet body and the oversheet body,
The sheet body includes a release film, an adhesive layer, and a sheet body base material in this order, and the oversheet body includes a receiving layer and an oversheet body base material,
Provided is a set of a sheet body and an oversheet body, wherein the adhesive layer comprises an acrylic polymer, an actinic ray polymerizable oligomer, a polymerization initiator, and a crosslinking agent. The

  In the aspect of the present invention, the acrylic polymer is preferably a copolymer of an acrylate ester and a hydroxyl group-containing monomer copolymerizable with the acrylate ester.

  In the aspect of the present invention, the acrylic polymer is preferably a copolymer of the acrylic ester and a hydroxyl group-containing monomer and a carboxyl group-containing monomer copolymerizable with the acrylic ester.

  In the embodiment of the present invention, the mass ratio of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 51:49 to 100: 0.

  In the aspect of this invention, it is preferable that the quantity of the said actinic-light polymerizable oligomer contained in an adhesive layer is 10 to 60 mass parts with respect to 100 mass parts of said acrylic polymers.

  In the embodiment of the present invention, it is preferable that the actinic ray-polymerizable oligomer has a mass average molecular weight (Mw) of 100,000 or more and 1.1 million or less.

  In the aspect of the present invention, the polymerization initiator has a weight reduction rate by thermogravimetry when the temperature is raised from 30 ° C. to 190 ° C. at a temperature raising temperature of 10 ° C./min and maintained at 190 ° C. for 30 minutes. It is preferable that it is 50% or less.

  In the aspect of this invention, it is preferable that the said sheet body is provided with the sheet | seat for repair or reinforcement between the said adhesive layer and the said base material.

  In the aspect of the present invention, it is preferable that the oversheet body includes a protective layer between the oversheet body substrate and the receiving layer.

  According to another aspect of the present invention, there is provided a method for producing a design sheet using a set of the sheet body and an oversheet body, the step of forming a print on a receiving layer provided in the oversheet body; And a step of laminating the receiving layer and a base material for a sheet body provided in the sheet body.

  In the other aspect of this invention, it is preferable to include the process of peeling the base material for oversheet bodies with which the said oversheet body is equipped.

  The design sheet produced using the set of the sheet body of the present invention and the oversheet body has a high adhesive force to the adherend, and it is easy to peel off without causing adhesive residue. Can be peeled off.

It is a cross-sectional schematic diagram of the sheet | seat body by one Embodiment of this invention. It is a cross-sectional schematic diagram of the oversheet body by one Embodiment of this invention. It is a cross-sectional schematic diagram showing one Embodiment of the design sheet | seat which can be produced using the set of this invention.

<Definition>
In the present specification, “part”, “%”, “ratio” and the like indicating the composition are based on mass unless otherwise specified. The actinic ray curable resin means a precursor or a composition before irradiation with actinic rays, and an actinic ray curable resin is obtained by curing an actinic ray curable resin by irradiating actinic rays. To do.

  In the present specification, the actinic ray means radiation that chemically acts on the actinic ray curable resin to promote polymerization, and specifically, visible light, ultraviolet ray, X-ray, electron beam. , Α ray, β ray, γ ray and the like.

<Sheet body>
The sheet body 1 of the present invention comprises a release film 2, an adhesive layer 3, and a sheet body substrate 4 in this order (see FIG. 1). In a preferred embodiment, the sheet body 1 includes a repair or reinforcing sheet (not shown) between the adhesive layer 3 and the sheet body substrate 4.

<Peeling film>
The release film is not particularly limited as long as the release film is provided on the surface of the adhesive layer so as to be peelable and has strength and flexibility enough to protect the adhesive layer, and various films are used. Can do. Examples of the release film material include polyester resins, polyvinyl resins, fluorine resins, polystyrene resins, polyacrylic resins, cellulose resins, polycarbonate resins, polyamide resins, and polyolefin resins such as polypropylene resins. Known resins such as polyvinyl alcohol resins, polyimide resins, phenol resins and polyurethane resins can be mentioned. Among these, polyester resins, polycarbonate resins, and polyolefin resins are preferable from the viewpoints of transparency, heat resistance, dimensional stability, rigidity, flexibility, stackability, cost, and the like.

  Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyarylate, and polytetramethylene terephthalate. In particular, polyethylene terephthalate is preferable from the viewpoint of ease of handling and cost.

  In addition, the synthetic resin film which used the said resin independently may be sufficient as a peeling film, and the synthetic resin film used combining 2 or more types of resin may be sufficient, and the synthesis | combination used individually or in combination. The composite film which laminated | stacked the resin film may be sufficient.

  Moreover, it is preferable that the surface at the side of the adhesive layer of a peeling film has been subjected to easy peeling treatment. Examples of the easy release treatment include providing an easy release layer (not shown) between the release film and the adhesive layer. The easy release layer can be formed by applying a release agent. The release agent is not particularly limited. For example, a water-soluble resin, a hydrophilic resin, a wax, a silicone resin, a fluorine resin, an aminoalkyd resin, a melamine resin, a polyester resin, an acrylic resin, or the like is used. be able to. The application method of the release agent is not particularly limited, and examples thereof include application methods such as roll coating, gravure coating, and spray coating.

  The release film surface is preferably preliminarily subjected to an easy-adhesion treatment for enhancing the adhesiveness with the easy-release layer. Examples of the easy adhesion treatment include corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, preheat treatment, dust removal treatment, vapor deposition treatment, and alkali treatment.

  The thickness of the release film is preferably 5 μm or more and 200 μm or less.

The method for producing the release film is not particularly limited, and for example, the release film can be produced by a method such as a solution casting method, a melt extrusion method, or a calendar method. In addition, you may use a commercial item for a peeling film.

<Adhesive layer>
The adhesive layer comprises an acrylic polymer, an actinic ray polymerizable oligomer, a polymerization initiator, and a crosslinking agent. The adhesive layer provided in the transfer sheet according to the present invention has high adhesive strength before irradiation with actinic light, and reduces the adhesive strength of the adhesive layer by irradiating with active light. And can be easily peeled off from the adherend.

(Acrylic polymer)
The acrylic polymer is not particularly limited, and examples thereof include an acrylic ester copolymer obtained by copolymerizing an acrylic ester and another monomer.

  Examples of the acrylate ester include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, hydroxylethyl acrylate, propylene glycol acrylate, acrylamide, and glycidyl acrylate. It is done. These can be used alone or in combination of two or more. In the present invention, among the above acrylic esters, n-butyl acrylate and 2-ethylhexyl acrylate are particularly excellent in transparency, heat resistance, moist heat resistance, durability, coating suitability, etc. This is preferable in terms of cost.

  Other monomers include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide, methacryl Examples include amide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and n-ethylhexyl methacrylate. These can be used alone or in combination of two or more. In the present invention, among the monomers, methacrylic acid-n-ethylhexyl is preferable.

  When the acrylic polymer is an acrylate copolymer, the mass average molecular weight (Mw) of the acrylate copolymer is not particularly limited as long as it exhibits a desired adhesive force, but is 100,000 or more, It is preferably 1.1 million or less, more preferably 200,000 or more and 900,000 or less. If it is the said range, sufficient adhesive force can be exhibited and it can be set as the adhesive layer of sufficient intensity | strength. The mass average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  In one embodiment, the acrylic polymer is obtained by copolymerization of an acrylate ester and a hydroxyl group-containing monomer copolymerizable with the acrylate ester. In one embodiment, the acrylic polymer is obtained by copolymerization of an acrylate ester, a hydroxyl group-containing monomer copolymerizable with the acrylate ester, and a carboxyl group-containing monomer. In this case, the mass ratio of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 51:49 to 100: 0, and more preferably 75:25 to 100: 0. By setting the mass ratio of the hydroxyl group-containing monomer to the carboxyl group-containing monomer in the acrylic polymer within the above range, an adhesive residue is generated when the transfer sheet attached to the adherend subjected to the etching treatment is peeled off. Can be prevented. In the above two cases, it is preferable that the main component is an acrylate ester. Here, the main component means that the copolymerization ratio is 51% by mass or more.

  The copolymerizable hydroxyl group-containing monomer is not particularly limited as long as it has a copolymerizable polymerizable group and a hydroxyl group in its structure. For example, 2-hydroxyethyl acrylate, 2-hydroxyacrylate Examples thereof include hydroxypropyl, 2-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, polyethylene glycol acrylate, and the like.

  The copolymerizable carboxyl group-containing monomer is not particularly limited as long as it has a copolymerizable polymerizable group and a carboxyl group in its structure. For example, acrylic acid, methacrylic acid, carboxyethyl ( Examples include meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

  The copolymerization ratio (mass ratio) between the acrylic ester and the copolymerizable hydroxyl group-containing monomer is not particularly limited as long as the acrylic ester is a main component, and is appropriately selected so as to exhibit a desired adhesive strength. Can be set.

(Actinic ray polymerizable oligomer)
The active light polymerizable oligomer is not particularly limited as long as it can be polymerized by irradiation with active light, and examples thereof include oligomers such as photo radical polymerizable, photo cationic polymerizable, and photo anionic polymerizable. . Among these, a photo-radically polymerizable oligomer is preferable. This is because the curing speed is high, and a wide variety of compounds can be selected. Furthermore, physical properties such as adhesiveness before curing and peelability after curing can be easily controlled to desired ones. . Examples of the radical photopolymerizable oligomer include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyol (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, and silicone-based. (Meth) acrylate etc. are mentioned, and these may be used alone or in combination of two or more.

  The mass average molecular weight (Mw) of the actinic ray-polymerizable oligomer is not particularly limited, but is preferably 100,000 or more and 1.1 million or less. If it is in the said range, desired adhesive force will be shown before actinic light irradiation, and it can peel easily, without adhesive residue remaining after actinic light irradiation. The mass average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  The amount of the actinic ray polymerizable oligomer contained in the adhesive layer is preferably 10 parts by mass or more and 60 parts by mass or less, and 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the acrylic polymer. It is more preferable that By adjusting the amount of the actinic ray polymerizable oligomer, it is possible to control the adhesive strength after the actinic ray irradiation. If it is in the said range, since the crosslinking density after actinic ray irradiation will become sufficient, suitable peelability can be implement | achieved. In addition, adhesive residue on the adherend due to a decrease in cohesive force hardly occurs.

  The adhesive layer may contain an actinic ray polymerizable monomer that can be polymerized by irradiation with actinic rays in addition to the actinic ray polymerizable oligomer. As such a monomer, a polyfunctional acrylate or a polyfunctional methacrylate is preferable. For example, trimethylol methane tri (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule, trimethylol ethanetri (meta) ) Acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene Examples thereof include oxides and propylene oxide adducts. When the adhesive layer contains these monomers, the crosslink density after irradiation with actinic rays becomes sufficient, so that suitable peelability can be realized. In addition, adhesive residue on the adherend due to a decrease in cohesive force hardly occurs.

  When the adhesive layer comprises an actinic ray polymerizable oligomer and an actinic ray polymerizable monomer, the total content is 10 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the acrylic polymer. It is preferably 20 parts by mass or more and 50 parts by mass or less. If these total content is in the said numerical range, since the crosslinking density after actinic ray irradiation will become sufficient, suitable peelability can be implement | achieved. In addition, adhesive residue on the adherend due to a decrease in cohesive force hardly occurs.

(Polymerization initiator)
When the adhesive layer contains a polymerization initiator, the sensitivity of the actinic ray polymerizable oligomer can be enhanced, and the polymerization curing time by actinic rays and the actinic ray irradiation amount can be reduced.

  The polymerization initiator contained in the adhesive layer of the transfer sheet according to the present invention was heated from 30 ° C. to 190 ° C. at a temperature rising rate of 10 ° C./min, and maintained at 190 ° C. for 30 minutes. The weight loss rate by thermogravimetry is 50% or less. The weight reduction rate is preferably 30% or less, more preferably 20% or less. Since the adhesive layer of the transfer sheet contains such a polymerization initiator, even if the adherend is exposed to a high temperature in a state where the transfer sheet is attached to the adherend, Decrease in adhesive strength can be prevented.

The weight reduction rate can be calculated from the weight measured using a commercially available thermogravimetric measuring device, for example, DTG-60A manufactured by Shimadzu Corporation. Specifically, the polymerization initiator is analyzed (atmosphere gas: nitrogen, gas flow rate: 50 ml / min, temperature range: 30 to 190 ° C., temperature rising condition: 10 ° C./min), and the polymerization initiator at 30 ° C. , And the weight (W2) of the polymerization initiator after 30 minutes from reaching 190 ° C. can be measured and applied to the following equation.
Weight reduction rate (%) = [(W1 (g) −W2 (g)) / W1 (g)] × 100

  As a commercial item of a polymerization initiator, Irgacure 754 (made by BASF Japan), Irgacure 2959 (made by BASF Japan), etc. are mentioned, for example.

  The amount of the polymerization initiator contained in the adhesive layer is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass in total of the acrylic polymer and the active light polymerizable oligomer. More preferably, it is 5 parts by mass or more and 3 parts by mass or less. If it is in the said range, actinic-light polymerizable oligomer can fully be hardened and appropriate peelability can be implement | achieved. In addition, when an adhesive layer contains an actinic-light-polymerizable oligomer and an actinic-light-polymerizable monomer, content of a polymerization initiator is the sum total of an acrylic polymer, an actinic-light-polymerizable oligomer, and an actinic-light-polymerizable monomer. The amount is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass.

(Crosslinking agent)
A crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an epoxy-type crosslinking agent, etc. can be used. As an isocyanate type crosslinking agent, for example, a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having a terminal isocyanate group obtained by reacting a polyisocyanate compound and a polyol compound, 3 of the urethane prepolymer Examples include masses. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3 -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like.

  Examples of the epoxy-based crosslinking agent include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diester. Examples thereof include polyfunctional epoxy compounds such as glycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutadiene diglycidyl ether.

  The said crosslinking agent can be used individually or in combination of 2 or more types, and can be suitably selected according to the kind etc. of an acrylic polymer.

  In addition, as a commercial item of the said isocyanate type crosslinking agent, L45 (made by Soken Chemical Co., Ltd.), TD75 (made by Soken Chemical Co., Ltd.), BXX5627 (made by Toyo Ink Manufacturing Co., Ltd.), X-301-422SK (Siden), for example. (Made by Kagaku Co., Ltd.) etc. can be used suitably. Moreover, as a commercial item of the said epoxy-type crosslinking agent, E-5XM (made by Soken Chemical Co., Ltd.), E-5C (made by Soken Chemical Co., Ltd.) etc. can be used suitably, for example.

  The amount of the cross-linking agent contained in the adhesive layer varies depending on the type of the cross-linking agent. Part or less, preferably 0.01 parts by weight or more and 10 parts by weight or less. If it is the said range, the adhesiveness of an adhesive layer and a base material can be improved.

  Moreover, in the case of an epoxy-type crosslinking agent, it is preferable that it is 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of acrylic polymers, and it is 0.01 mass part or more and 10 mass parts or less. More preferred. If it is the said range, the adhesive force and cohesion force before actinic ray irradiation can be controlled to desired intensity | strength.

(Other)
The adhesive layer is a silane coupling agent, a tackifier, a metal chelating agent, a surfactant, an antioxidant, an ultraviolet absorber, a pigment, a dye, as necessary, as long as the object of the present invention is not impaired. In addition, various additives such as a colorant, an antistatic agent, an antiseptic, an antifoaming agent, and a wettability adjusting agent may be included.

<Base material for sheet body>
As the base material for the sheet body, any material having heat resistance capable of withstanding the thermal energy (for example, heat of the thermal head) when transferring the printed material from the transfer sheet or the like to the receiving layer of the transfer medium is used. It can be used without any particular limitation. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene naphthalate coextruded film , Polyamide resins such as nylon-6, nylon-6,6, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polyvinyl resins such as polyvinyl chloride, polyacrylate, polymethacrylate, polymethyl methacrylate, etc. Polyacrylic resin, polyimide resin such as polyimide and polyetherimide, polyarylate, polysulfone, polyether Engineering resins such as sulfone, polyphenylene ether, polyphenylene sulfide, polyaramid, polyether ketone, polyether nitrile, polyether ether ketone, polyether sulfite, polystyrenes such as polycarbonate, polystyrene, high impact polystyrene, AS resin, ABS resin A film produced using a cellulose-based resin such as resin, cellophane, cellulose acetate, or nitrocellulose can be used. Among these, films made of polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and films made of polyolefin resins such as polyethylene, polypropylene, and polymethylpentene are preferable because of excellent heat resistance and mechanical strength. In addition, a polyethylene terephthalate film and a polypropylene film are preferable because they have high transparency and do not hinder ultraviolet irradiation on the adhesive layer when the design sheet is peeled off from the adherend. The base material for the sheet body is not limited to the film as described above, and high-quality paper, coated paper, resin-coated paper, art paper, cast-coated paper, paperboard, and the like can also be used. Moreover, the composite sheet which laminated | stacked two or more of these can also be used.

  Moreover, in one Embodiment, it is preferable to make the base material for sheet bodies into the porous film which has a fine space | gap (micro void). By making the base material for sheet bodies into a porous film, when it is set as the design film mentioned later, the visibility of the printed matter on a receiving layer improves more.

  The base material for a sheet body may be a copolymer resin or a mixture (including an alloy) containing the above-mentioned resin as a main component, or a laminate composed of a plurality of layers. Moreover, although the base material for sheet bodies may be a stretched film or an unstretched film, the film extended | stretched to the uniaxial direction or the biaxial direction is preferable in order to improve an intensity | strength. In addition, surface treatment such as corona treatment and primer treatment is applied to the surface of the base material for sheet body in order to improve the adhesion between the base material for sheet body and the receiving layer and between the base material and the adhesive layer. Is preferred.

  The thickness of the base material for sheet is preferably 1 μm or more and 300 μm or less, and more preferably 20 μm or more and 100 μm or less. If the thickness of the substrate is within the above numerical range, sufficient heat resistance can be ensured and actinic ray irradiation is not hindered.

<Repair and reinforcement sheets>
The sheet body may include a repair or reinforcement sheet between the adhesive layer and the sheet body base material, as desired. The sheet for repair or reinforcement is not particularly limited as long as the sheet can repair or reinforce the concrete structure. For example, the sheet | seat which can prevent the penetration | invasion of the factor (deterioration factor) which degrades a concrete structure may be sufficient, and the sheet | seat which can reinforce the object which the intensity | strength is falling may be sufficient. Furthermore, it may be a sheet having functions other than these and capable of repairing or reinforcing the object, or a sheet satisfying all of these.

  More specifically, as a sheet for repair or reinforcement, for example, a synthetic resin film is used as a base material, a resin material layer is provided on one surface of the base material, and a fiber material layer is provided on the other surface of the base material. What was provided can be mentioned.

  Examples of synthetic resin film materials include polyester resins, polypropylene resins, polyvinyl resins, fluorine resins, polystyrene resins, polyacrylic resins, cellulose resins, polycarbonate resins, polyamide resins, and polyolefin resins. , Polyvinyl alcohol resin, polyimide resin, phenol resin, polyurethane resin, and the like.

  The resin material layer acts to prevent the concrete structure and the bonded portion between the surface of the concrete structure and the adhesive layer from being damaged by external deterioration factors. Examples of the deterioration factor include water, oxygen, carbon dioxide gas, and chloride ions. Examples of the resin constituting the resin material layer include fluorine resins, acrylic resins, acrylic silicone resins, acrylic fluorine resins, silicone resins, urethane resins, and chlorine resins. One type or two or more types can be used.

  Examples of the fiber material layer include one or more selected from woven fabric, knitted fabric, nonwoven fabric, laminated fabric, synthetic resin foam, paper, and the like. Examples of the optical material for the fiber material layer include polyester fiber, polyamide fiber, aramid fiber, vinylon fiber, carbon fiber, glass fiber, and polyolefin fiber. One or two selected from these can be used. More than seeds can be used. Among these, polyester fiber, polyamide fiber, aramid fiber, vinylon fiber, and polyolefin fiber are preferable because they are light and excellent in strength. These fibers may be blended, may be used properly for warp and weft, or may be laminated in multiple layers.

  The thickness of the sheet for repair or reinforcement varies depending on whether it is used for repair or for reinforcement, but is usually in the range of 0.01 mm or more and 1.0 mm or less.

  The sheet for repair and reinforcement can be produced, for example, by a method including a step of providing a resin material layer on one surface of a substrate and a step of providing a fiber material layer on the other surface of the substrate. The resin material layer can be formed, for example, by applying the above-described constituent resin on a substrate and then curing the resin. The fiber material layer can be formed by applying a composite material including a fiber material and a resin such as a polyester-based resin on a base material and curing the resin.

<Oversheet body>
The oversheet body 5 of the present invention includes a receiving layer 6 and a substrate 7 for an oversheet body (see FIG. 2). In a preferred embodiment, the oversheet body 5 may include a protective layer or a heat insulating layer (not shown) between the receiving layer 6 and the oversheet body substrate 7. In a more preferred embodiment, the oversheet body 5 includes a release layer (not shown) between the receiving layer 6 or the protective layer and the oversheet body substrate 7.

<Receptive layer>
As a material for forming the receiving layer, a conventionally known resin material that can easily receive a heat transferable color material such as a sublimation dye or a heat-meltable ink can be used. For example, polyolefin resin such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer or polyvinyl acrylate such as polyacrylate, polyethylene terephthalate or Use polyester resins such as polybutylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene or propylene and other vinyl polymers, cellulose resins such as ionomers or cellulose diastases, polycarbonates, etc. Among these, vinyl chloride-vinyl acetate copolymer or polyvinyl chloride is preferable, and vinyl chloride-vinyl acetate copolymer is particularly preferable.

The thickness of the receiving layer is not particularly limited, but when forming the receiving layer, the coating amount of the receiving layer coating solution is preferably 0.5 g / m ² or more and 10 g / m ² or less in a dry state. .

  The receiving layer is a receiving layer coating solution prepared by adding one or more materials selected from the above-mentioned materials and various additives as necessary, and dissolving or dispersing them in an appropriate solvent such as water or an organic solvent. Can be applied and dried by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate.

<Base material for oversheet>
The substrate for the oversheet body is not particularly limited as long as it has heat resistance that can withstand the thermal energy (for example, heat of the thermal head) when transferring the printed material from the transfer sheet or the like to the receiving layer. The film used as a base material for sheet bodies can be used similarly. In addition, it is not restricted to these films etc., A patch can also be used as a base material for oversheet bodies. The durability is further improved by the oversheet body substrate being a patch. The patch is particularly transparent if it is transparent, does not adversely affect the visibility of the printed matter on the receiving layer, and does not interfere with ultraviolet irradiation of the adhesive layer when the design sheet is peeled off from the adherend. For example, those made of polyethylene terephthalate or polyester can be used.

<Protective layer>
Next, the protective layer provided in the oversheet body as desired will be described. A protective layer bears protection of the printed matter on the receiving layer with which the design film produced by laminating | stacking a sheet body and an oversheet body is equipped.

  The protective layer is composed of polyester resin, polycarbonate resin, polyacrylic resin, polyurethane resin, polyamide resin, polyvinyl resin, silicone-modified resin of these resins, actinic ray curable resin, ultraviolet absorption And a mixture thereof. Moreover, it is preferable that a protective layer is a thing with high transparency so that it may not interfere with the ultraviolet irradiation with respect to the adhesive layer at the time of peeling a design sheet from a to-be-adhered body.

  In one embodiment, the protective layer preferably comprises two or more resins having different number average molecular weights (Mn). More preferably, the sum (Σ) when adding the values obtained by integrating the Mn of the resin contained in the protective layer by the content ratio (mass basis) of each resin is preferably 3000 or more and 17000 or less. When the total sum (Σ) is within the above numerical range, the durability of the protective layer can be improved.

  The protective layer includes a polyester resin A having a total sum (Σ) within the above numerical range, a Mn of 2000 or more and 10,000 or less, and a Mn of greater than 10,000 and a polyester resin B of 25,000 or less. Is preferred. When the protective layer contains the resin, durability of the protective layer can be further improved. The content of the polyester resin A in the protective layer is preferably 10% by mass or more and 70% by mass or less, and preferably 30% by mass or more and 70% by mass with respect to the total amount of the polyester resin A and the polyester resin B. It is more preferable that the amount is not more than mass%.

  Moreover, it is preferable that a protective layer comprises the polyester resin A1 whose Mn is 2000 or more and 4000 or less and the polyester resin A2 whose Mn is larger than 4000 and 10,000 or less as the polyester resin A. The content of the polyester resin A1 in the protective layer is preferably 5% by mass or more and 65% by mass or less with respect to the total amount of the polyester resin A1, the polyester resin A2, and the polyester resin B. The content of the polyester resin A2 in the protective layer is preferably 5% by mass or more and 65% by mass or less with respect to the total amount of the polyester resin A1, the polyester resin A2, and the polyester resin B.

  In one embodiment, the protective layer preferably comprises an actinic ray curable resin from the viewpoint of durability. The actinic ray curable resin contains a polymer, a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond such as (meth) acryloyl group and (meth) acryloyloxy group or an epoxy group in the molecule as a polymerization component. It comprises a suitably mixed composition and the like.

  Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelin. Polybasic acids such as acid, sebacic acid, dodecanoic acid, tetrahydrophthalic acid, ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by the combination of polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol. (Meth) acrylates, for example, epoxy (meth) acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid For example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate, xylene diisocyanate, 1,2-polybutadiene glycol, tolylene Isocyanate, 2-hydroxyethyl acrylate, trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxy Urethane (meth) acrylate in which (meth) acrylic acid is introduced into urethane resin like til acrylate, for example, silicone resin acrylate such as polysiloxane (meth) acrylate, polysiloxane diisocyanate, 2-hydroxyethyl (meth) acrylate Other examples include alkyd-modified (meth) acrylates in which a (meth) acryloyl group is introduced into an oil-modified alkyd resin, and spirane resin acrylates.

  Examples of the monomer or oligomer include 2-ethylhexyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl ( (Meth) acrylate, tetrahydrofurfuryloxyethyl (meth) acrylate, tetrahydrofurfuryloxyhexanolide (meth) acrylate, (meth) acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane ( Monofunctional (meth) acrylates such as (meth) acrylate, or itaconic acid esters obtained by replacing these (meth) acrylates with itaconate, crotonate, or maleate, Rotonic acid esters, maleic acid esters, such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, hexane Diol (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol hydroxypivalate, di (meth) acrylate of neopentyl glycol adipate, hydroxy Di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol pivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxy Til-5-ethyl-1,3-dioxane di (meth) acrylate, tricyclodecane dimethylol (meth) acrylate, ε-caprolactone adduct of tricyclodecane dimethylol (meth) acrylate, 1,6-hexanediol Difunctional (meth) acrylates such as diglycidyl ether di (meth) acrylate, or itaconic acid, crotonate, maleate in which these (meth) acrylates are replaced by itaconate, crotonate, maleate, Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meta ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone adduct of dipentaerythritol hexa (meth) acrylate, pyrogallol tri (meth) Polyfunctional (meth) acrylates such as acrylate, propionic acid / dipentaerythritol tri (meth) acrylate, propionic acid / dipentaerythritol tetra (meth) acrylate, hydroxypivalylaldehyde-modified dimethylolpropane tri (meth) acrylate, or these Itaconic acid ester, crotonic acid ester, maleic acid ester, phosphine Zen monomer, triethylene glycol, isocyanuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, trimethylolpropane (meth) acrylic acid benzoate , Alkylene glycol type (meth) acrylic acid modified, urethane modified (meth) acrylate and the like.

  The protective layer may contain a filler. Examples of the filler include organic fillers, inorganic fillers, and organic-inorganic hybrid fillers. The filler may be a powder or a sol. From the viewpoint of dispersibility, inorganic particles are preferable among the fillers described above.

  The filler contained in the protective layer preferably has an average particle size of 1 nm or more and 200 nm or less, more preferably 1 nm or more and 50 nm or less, and further preferably 7 nm or more and 25 nm or less. By keeping the average particle diameter of the filler within the above numerical range, the dispersibility can be maintained while maintaining the transparency of the protective layer, and the stability of the protective layer coating solution is prevented from being lowered. Can do. The “average particle size” means the volume average particle size, and is measured by a known method using a particle size distribution / particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device, manufactured by Nikkiso Co., Ltd.). can do.

  Examples of the inorganic particles include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, etc., and improved wear resistance. From this viewpoint, it is preferable to use silica particles. Furthermore, it is preferable that the inorganic particles have been subjected to a surface treatment using a silane coupling agent such as γ-aminopropyltriethoxysilane or γ-methacryloxypropyltrimethoxysilane.

  The filler is preferably contained in an amount of 10% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 45% by mass or less, based on the total solid content in the protective layer. More preferably, it is contained in an amount of not less than 40% by mass and not more than 40% by mass.

  The thickness of the protective layer is preferably 1 μm or more and 8 μm or less, more preferably 2 μm or more and 6 μm or less. If the thickness of the protective layer is within the above numerical range, it is possible to impart sufficient hard coat performance and plasticizer performance while preventing transfer defects such as foil breakage, tailing and burrs, and during the transfer of the protective layer. Transfer defects such as paper peeling and chipping can be prevented.

  When the protective layer does not contain an actinic ray curable resin, the coating solution containing the resin is received by a known means such as roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod coat, etc. It can be formed by coating and drying on the layer. When the actinic ray curable resin is contained, the coating solution containing the actinic ray curable resin as described above is applied on the receiving layer by the above means to form a coating film, and the actinic ray is used as described above. It can be formed by crosslinking and curing a polymerization component such as a polymerizable copolymer. For example, a conventionally known ultraviolet irradiation device can be used for the irradiation of ultraviolet rays, and various types such as a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an electrodeless ultraviolet lamp, and an LED are used without limitation. be able to. For the electron beam irradiation, either a high energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or more and 300 keV or less, or a low energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or less is used. The irradiation method may be either a scanning type or a curtain type irradiation device. A polymerization initiator may be added to the coating solution. The protective layer can also be formed by previously forming on a substrate or the like, placing it as a transfer sheet, and transferring it onto the receiving layer.

<Insulation layer>
Moreover, the oversheet body may include a heat insulating layer between the receiving layer and the base material or between the receiving layer and the protective layer, if desired. The heat insulating layer has a heat insulating property capable of preventing heat applied at the time of forming a printed product by heat transfer onto the receiving layer from being lost due to heat transfer to a substrate or the like. The heat insulating layer is preferably a hollow layer or a porous layer.

The hollow layer contains hollow particles, and may further contain a hydrophilic binder and other additives. When the porous layer comprises hollow particles, the cushioning property of the porous layer is improved. The degree of cushioning property of the porous layer can be changed by changing the thickness of the porous layer. The thickness of a porous layer is not specifically limited, For example, it can be 10 micrometers or more and 100 micrometers or less. The density of the porous layer is preferably 0.1 g / cm ³ or more and 0.8 g / cm ³ or less, more preferably 0.2 g / cm ³ or more and 0.7 g / cm ³ or less. preferable.

  The average particle diameter of the hollow particles is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.3 μm or more and 5 μm or less. If the average particle diameter of the hollow particles is within the above numerical range, the heat insulation and cushioning properties of the porous layer can be improved. Moreover, the average hollowness of the hollow particles is preferably 20% or more, and more preferably 30% or more. Moreover, it is preferable that it is 70% or less. Furthermore, the hollow particles may be any of organic hollow particles composed of resin or the like, inorganic hollow particles composed of glass or the like, and crosslinked hollow particles.

  The porous layer is made of a porous film. The thickness of the porous film is preferably 10 μm or more and 100 μm or less, more preferably 15 μm or more and 80 μm or less, and further preferably 20 μm or more and 50 μm or less. In a preferred embodiment, the porous film is preferably a porous film having fine voids (microvoids) containing a polypropylene resin as a base resin.

<Release layer>
The oversheet body may further include a release layer between the oversheet body substrate and the receiving layer or the protective layer, if desired. Examples of the resin used for the release layer include melamine resin, silicone, fluorine resin, cellulose resin, urea resin, polyolefin resin, acrylic resin, and fiber resin. Among these, a melamine-based resin is preferable because an appropriate adhesive force between the substrate and the transfer layer can be imparted to the transfer foil.

  Usually, the thickness of the release layer is preferably in the range of 0.1 to 5 μm, and more preferably in the range of 0.5 to 2 μm.

<Production of design sheet>
In one embodiment, the design sheet 10 forms a printed matter (not shown) by thermal transfer from a thermal transfer sheet having a color material layer on the receiving layer 6 included in the oversheet body 5 by thermal transfer. The layer 6 can be obtained by laminating the sheet body 1 on the sheet body substrate 4 included in the sheet body 1 (see FIG. 3). In a preferred embodiment, the substrate for oversheet body is peeled after lamination (not shown). As for the design sheet produced in this way, the printed matter is more formed on the substrate side for the sheet body, and the durability is improved.

  The design sheet obtained as described above can be adhered to a target by peeling off the release film and attaching the exposed adhesive layer to a concrete structure. In that case, it is preferable to pressure-bond the adhesive layer with which a design sheet is provided using a roller etc. to object.

  In one embodiment, the design sheet can be adhered to the object by heat-curing before or simultaneously with the adhesion of the adhesive layer or after the adhesion. Although heating temperature is based also on the kind of hardening | curing agent to be used, etc., they are 100 degreeC or more and 150 degrees C or less.

The design sheet adhered to the object can be easily peeled off from the object by irradiating with actinic rays such as ultraviolet rays and electron beams. As an irradiation condition of ultraviolet rays, for example, a condition in which the integrated light amount is about 1000 mJ / cm ^{2 in} a wavelength region of 300 nm or more and 370 nm or less can be exemplified. Moreover, as an electron beam irradiation condition, the conditions of about 50 kGy or more and 100 kGy or less can be mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
<Production of sheet body>
A 30 μm-thick polypropylene film (Futamura Chemical Co., Ltd., trade name: FOS-BT # 30) is used as a substrate for a sheet body, and an adhesive layer coating liquid A having the following composition is formed on the substrate. After coating the entire surface with an applicator, it was dried in a drying oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 150 μm.
<Adhesive layer coating liquid A>
UV-curable acrylic pressure-sensitive adhesive 100 parts (solid content: 40%, manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: N-4498, acrylic polymer + active light polymerizable oligomer, mass average molecular weight of acrylic polymer: about 40 Actinic light polymerizable oligomer: polyurethane acrylate, mass ratio of hydroxyl group-containing monomer to carboxyl group-containing monomer in acrylic polymer: 30/1)
・ Polymerization initiator 1.4 parts (photo radical generator, solid content: 100%, manufactured by BASF Japan, trade name: Irgacure 754)
・ Crosslinking agent 1.5 parts (isocyanate-based crosslinking agent, solid content 75%, manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate L)
180 parts of a mixed solvent of toluene and methyl ethyl ketone (mass ratio 1: 1, manufactured by DIC Graphics, trade name: KT11)

  Next, as a release film, a polypropylene film having a thickness of 100 μm (manufactured by Toyobo Co., Ltd., trade name: Crisper G1212) was laminated on the adhesive layer to obtain a sheet body.

<Production of oversheet body>
On a 12 μm-thick patch (manufactured by JVC, trade name: CY-R10FC-60), a receiving layer coating solution having the following composition is coated with a gravure coating to a coating amount of 2.0 g / m ^{2 in} a dry state. After coating as described above, it was dried to form a receiving layer to obtain an oversheet body.
<Receptive layer coating solution composition>
・ 95 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name: CNL)
・ Epoxy-modified silicone oil 5 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U)
・ Toluene 200 parts ・ MEK 200 parts

<Production of design sheet>
On the receiving layer of the obtained oversheet body, the thermal transfer sheet A produced as follows was transferred using the following test printer.
(Test printer)
Thermal head: KEE-57-12GAN2-STA (manufactured by Kyocera Corporation)
Heating element average resistance: 3303 (Ω)
Main scanning direction printing density: 300 dpi
Sub-scanning direction printing density: 300 dpi
Printing voltage: 18 (V)
1 line cycle: 1.5 (msec.)
Printing start temperature: 35 (℃)
Pulse duty ratio: 85%

<Preparation of thermal transfer sheet A>
Using a polyethylene terephthalate film with a thickness of 4.5 μm as the base material and subjected to easy adhesion treatment, a coating solution for the back layer having the following composition was applied on the back surface to a dry weight of 0.8 g / m ^2. A layer was formed. Next, on the other surface of the base material, a yellow dye layer coating liquid 1 having the following composition, a magenta dye layer coating liquid 1 having the following composition, and a cyan dye layer coating liquid 1 having the following composition are respectively dried. The thermal transfer sheet was produced by coating in the order of coating so that the coating amount was 0.6 g / m ² to form a yellow dye layer, a magenta dye layer, and a cyan dye layer.

<Back layer coating liquid>
-Polyvinyl butyral resin 2.0 parts (Sekisui Chemical Co., Ltd., trade name: ESREC BX-1)
・ 9.2 parts of polyisocyanate (Dainippon Ink Chemical Co., Ltd., trade name: Burnock D750)
・ Phosphate surfactant 1.3 parts (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf A208N)
・ Talc 0.3 parts (Nippon Talc Industry Co., Ltd., trade name: Microace P-3)
・ Toluene 43.6 parts ・ Methyl ethyl ketone 43.6 parts

<Yellow dye layer coating solution 1>
-6.0 parts of yellow dye represented by the following general formula (1)-4.0 parts of polyvinyl acetoacetal resin
(Product name: KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Silicon 0.1 parts (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-3939)
・ Toluene 45 parts ・ Methyl ethyl ketone 45 parts

<Coating liquid 1 for magenta dye layer>
-7.0 parts of magenta dye represented by the following general formula (2)-7.0 parts of polyvinyl acetoacetal resin
(Product name: KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Silicone 1.4 parts (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-3939)
・ Toluene 45 parts ・ Methyl ethyl ketone 45 parts

<Cyan dye layer coating solution 1>
-5.0 parts of cyan dye represented by the following general formula (3)-5.0 parts of polyvinyl acetoacetal resin
(Product name: KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Silicon 0.1 parts (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-3939)
・ Toluene 45 parts ・ Methyl ethyl ketone 45 parts

  After the transfer, the receiving layer included in the oversheet body and the base material for the sheet body included in the sheet body were laminated, and a design sheet was produced from the set of the sheet body and the oversheet body.

(Example 2)
<Production of oversheet body>
Using a film in which a release layer of a melamine resin is applied to one side of a polyethylene terephthalate film having a thickness of 12 μm as a base material, a protective layer coating solution having the following composition is formed on the release layer by gravure coating. Then, after applying and drying so that the thickness after drying becomes 6 μm, using a UV exposure device (H bulb use, reflector is cold type, LH10 lamp, manufactured by Fusion UV Systems Japan, trade name: F600V) Ultraviolet rays were irradiated to form a protective layer. Next, the receiving layer coating solution used in Example 1 was applied on the protective layer, and then dried to form a receiving layer to obtain an oversheet body.
<Protective layer coating solution composition A>
・ 40 parts of polyfunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300)
・ 25 parts of urethane acrylate (bifunctional, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
・ Acrylic copolymer 30 parts ・ Photopolymerization initiator 5 parts (Ciba Specialty Chemicals, trade name: Irgacure 907)
Filler (crosslinked polymethyl methacrylate) 5 parts (average particle size 5 μm, manufactured by Sekisui Plastics Co., Ltd., trade name: MBX-5)
・ Toluene 200 parts ・ MEK 200 parts

<Production of design sheet>
Transferred onto the receptor layer of the obtained oversheet body in the same manner as in Example 1, and after transfer, the receptor layer provided in the oversheet body, and the sheet body substrate provided in the sheet body produced in Example 1 Then, the polyethylene terephthalate film was peeled from the laminate of the sheet body and the oversheet body to prepare a design sheet.

Example 3
The protective layer coating liquid used in Example 2 is the following protective layer coating liquids b1 to b3, and the content ratio (mass basis) of each binder resin is 0.25: 0.25: b1: b2: b3. By changing to the protective layer coating liquid B kneaded so as to be 0.5, and coating on the oversheet substrate so that the coating amount is 4.5 g / m ² in a dry state. A design sheet was obtained in the same manner as in Example 2 except that a protective layer was formed.
<Protective layer coating solution b1>
20 parts of polyester resin (number average molecular weight: 3000, Tg = 53 ° C., manufactured by Toyobo Co., Ltd., trade name: Byron 220)
・ Toluene 40 parts ・ MEK 40 parts <Protective layer coating liquid b2>
20 parts of polyester resin (number average molecular weight: 10,000, Tg = 60 ° C., manufactured by Toyobo Co., Ltd., trade name: Byron GK-250)
・ Toluene 40 parts ・ MEK 40 parts <Protective layer coating liquid b3>
20 parts of polyester resin (number average molecular weight: 3000, Tg = 53 ° C., manufactured by Toyobo Co., Ltd., trade name: Byron 220)
・ Toluene 40 parts ・ MEK 40 parts

Example 4
A design sheet was obtained in the same manner as in Example 1 except that the composition of the adhesive layer coating solution was changed to the following.
<Adhesive layer coating solution B>
UV-curable acrylic pressure-sensitive adhesive 100 parts (solid content: 41%, manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: N-7257, acrylic polymer + activatable light polymerizable oligomer, mass average molecular weight of acrylic polymer: about 40 Actinic light polymerizable oligomer: polyurethane acrylate, mass ratio of hydroxyl group-containing monomer to carboxyl group-containing monomer in acrylic polymer: 3/1)
・ 1.4 parts of polymerization initiator (photo radical generator, solid content: 100 parts by mass, manufactured by BASF Japan, trade name: Irgacure 754)
・ Crosslinking agent 1.5 parts (isocyanate-based crosslinking agent, solid content 75%, manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate L)
180 parts of a mixed solvent of toluene and methyl ethyl ketone (mass ratio 1: 1, manufactured by DIC Graphics, trade name: KT11)

(Example 5)
The base material for the sheet body is a polypropylene film having a thickness of 60 μm (FOS-BT # 60, manufactured by Phutamura Chemical Co., Ltd.), and the release film is a polyethylene terephthalate film having a thickness of 38 μm (manufactured by Mitsubishi Plastics, Inc., trade name: A design sheet was produced in the same manner as in Example 2 except that S100-38) was used.

(Comparative Example 1)
Acrylic resin (modified methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer into which a hydroxyl group has been introduced, Tg: -42 ° C., manufactured by Arkema, Inc., contained in the adhesive layer coating liquid A of Example 1 : M22N) was changed to another acrylic resin (ethyl acrylate-methyl methacrylate copolymer, Tg: 18 ° C., manufactured by Negami Kogyo Co., Ltd., trade name: W-197C) in the same manner as in Example 1. A design sheet was prepared.

<Initial adhesion test>
The design sheets obtained in Examples 1 to 5 and Comparative Example 1 were cut into a width of 25 mm and a length of 100 mm to prepare test pieces. In addition, a polyimide film (film thickness: 50 μm, manufactured by Toray DuPont, trade name: Kapton 200H) was immersed in a ferric chloride solution at 60 ° C. for 2 minutes, and then washed twice with distilled water for 30 seconds. It was air-dried and the sticking object (the polyimide film which carried out the etching process) was produced.
The release film of the test piece was peeled off, laminated on the etched polyimide film surface using a 2 kg roller, and allowed to stand at room temperature and humidity for 20 minutes. Then, using a universal material testing machine (model 5565, manufactured by Instron Japan), the adhesive strength was measured (JIS Z0237 compliant, peeling speed: 300 mm / min, peeling distance: 50 mm, peeling angle: 180 °), Evaluation tests were conducted according to the following evaluation criteria.
A: The adhesive strength was 0.8 N / 25 mm or more and 15 N / 25 mm or less.
X: The adhesive strength was less than 0.8 N / 25 mm or more than 15 N / 25 mm.

<Measurement of adhesive strength after heat treatment>
The release sheet of the test piece was peeled off, laminated on the etched polyimide resin surface using a 2 kg roller, and allowed to stand at room temperature and humidity for 20 minutes. Next, after heating at 150 ° C. for 90 minutes, the sample is allowed to stand at room temperature and humidity for 1 hour, and the adhesive strength after heat treatment is measured using a universal material testing machine (model 5565, manufactured by Instron Japan). (In accordance with JIS Z0237, peeling speed: 300 mm / min, peeling distance: 50 mm, peeling angle: 180 °), an evaluation test was performed according to the following evaluation criteria.
A: The adhesive strength was 0.8 N / 25 mm or more and 20 N / 25 mm or less.
X: The adhesive strength was less than 0.8 N / 25 mm or more than 20 N / 25 mm.

<Adhesive residue test>
The release sheet of the test piece was peeled off, laminated on the etched polyimide film using a 2 kg roller, left at room temperature and humidity for 20 minutes, and then heated at 150 ° C. for 90 minutes. The test piece was peeled from the polyimide film after irradiating ultraviolet rays (integrated light quantity: 200 mj / cm ² ) using a fusion H / bulb lamp as a light source from the substrate side. The presence or absence of adhesive residue on the polyimide film surface after peeling the test piece was confirmed with an optical microscope (manufactured by Keyence Corporation, magnification 200 times, VHS-600).
○: There is no adhesive residue.
X: There is adhesive residue.

<Durability test (Taber test)>
For the prints on the receiving layer provided in the design sheets obtained in Examples 1 to 5 and Comparative Example 1, the wear wheel: CS-10F was used with a Taber abrasion tester, and the wear wheel was loaded every 250 times with a load of 500 gf. Was polished for a total of 1000 times. The surface condition was visually observed after polishing, and an evaluation test was performed according to the following evaluation criteria.
A: The image after 1000 cycles is good. ○: The image after 1000 cycles is good. Δ: The image after 1000 cycles is not good, but there is no practical problem. X: The image after 1000 cycles. Is bad

DESCRIPTION OF SYMBOLS 1 Sheet body 2 Release film 3 Adhesive layer 4 Base material for sheet body 5 Oversheet body 6 Receiving layer 7 Base material for oversheet body 10 Design sheet

Claims (11)

A set of a sheet body and an oversheet body, used to produce a design sheet by superimposing a sheet body and an oversheet body,
The sheet body includes a release film, an adhesive layer, and a sheet body base material in this order, and the oversheet body includes a receiving layer and an oversheet body base material,
The set of a sheet body and an oversheet body, wherein the adhesive layer comprises an acrylic polymer, an actinic ray polymerizable oligomer, a polymerization initiator, and a crosslinking agent.   The set according to claim 1, wherein the acrylic polymer is a copolymer of an acrylic ester and a hydroxyl group-containing monomer copolymerizable with the acrylic ester.   The set according to claim 1, wherein the acrylic polymer is a copolymer of the acrylic ester and a hydroxyl group-containing monomer and a carboxyl group-containing monomer copolymerizable with the acrylic ester.   The set according to claim 3, wherein a mass ratio of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is 51:49 to 100: 0.   The amount of the actinic ray polymerizable oligomer contained in the adhesive layer is 10 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the acrylic polymer. Set described in.   The set as described in any one of Claims 1-5 whose mass mean molecular weights (Mw) of the said actinic-light polymerizable oligomer are 100,000 or more and 1.1 million or less.   The polymerization initiator is heated at 30 ° C. to 190 ° C. at a temperature rising temperature of 10 ° C./min, and the weight reduction rate by thermogravimetry when maintained at 190 ° C. for 30 minutes is 50% or less. Item 7. The set according to any one of Items 1 to 6.   The set as described in any one of Claims 1-7 with which the said sheet | seat body is provided with the sheet | seat for repair or reinforcement between the said adhesive layer and the said base material.   The set according to any one of claims 1 to 8, wherein the oversheet body includes a protective layer between the oversheet body substrate and the receiving layer. A method for producing a design sheet using a set of the sheet body according to any one of claims 1 to 9 and an oversheet body,
Forming a printed matter on a receiving layer provided in the oversheet body;
Laminating the receiving layer and a sheet body base material provided in the sheet body.   The method of Claim 10 including the process of peeling the base material for oversheet bodies with which the said oversheet body is provided.

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